Substituted N-nitroaniline compounds and inorganic and organic salts thereof useful for enhancing auxiliary branching, canopy flowering and crop yield of plant and as lodging inhibitors therefor

ABSTRACT

There are provided di- tri- and tetrasubstituted N-nitroaniline compounds and inorganic and organic salts thereof which are effective for increasing axillary branching, improving canopy and enhancing flowering of herbaceous ornamental plants and graminaceous crops, leguminous crops, cotton and sunflowers. The salts are also effective as yield enhancing agents and lodging inhibitors for the crops.

The invention is the use of plant regulating substituted N-nitroanilines represented by formulae (I) and (Ia) below: ##STR1## wherein n is an integer of 0 or 1; R₁ is hydrogen, C₁ -C₃ alkyl, C₁ -C₃ haloalkyl, CN, halogen, NO₂, SO₂ R₈, COR₉, phenyl or substituted phenyl and the substituents are CH₃, CF₃, CH₃ O, halogen, NO₂ or OCH₂ --CO₂ C₂ H₅ ; R₂ and R₆ are hydrogen, halogen, C₁ -C₄ alkyl, C₁ -C₄ haloalkyl, C₁ -C₄ haloalkoxy, SO₂ R₈, SR₈ or COR₁₀ ; R₃ is hydrogen, C₁ -C₄ alkyl, C₁ -C₄ alkoxy, NH₂, NH--COCH₃, halogen, NO₂, SO₂ R₈, CN or CO₂ CH₃ ; R₄ is hydrogen, halogen, C₁ -C₂ alkyl, SO₂ R₈, SR₈, OCF₃, COR₉, CN, NH--COCH₃, SO₂ NR₁₀ R₁₁, ##STR2## phenoxy or substituted phenoxy and the substituents are CH₃, CF₃, CH₃ O, halogen, NO₂ or OCH₂ CO₂ C₂ H₅ ; R₅ is hydrogen, C₁ -C₃ alkyl or halogen; R₇ is hydrogen, C₁ -C₁₂ alkyl optionally substituted with halogen or CN, C₃ -C₄ alkenyl, C₃ -C₄ alkynyl, the methyl esters of lower alkanoic acids or the moiety ##STR3## wherein o is an integer of 0, 1,2 or 3, and the moiety may optionally be substituted with halogen, C₁ -C₂ alkyl, C₁ -C₂ alkoxy, (C₁ -C₃ alkyl)₃ SiCH₂ -- or NO₂ ; R₈ is C₁ -C₆ alkyl, phenyl or benzyl; R₉ is hydrogen, hydroxyl, C₁ -C₃ alkyl, C₁ -C₃ alkoxy or phenyl; R₁₀ and R₁₁ each are hydrogen, C₁ -C₄ alkyl or phenyl; with the proviso that not less than two and not more than four of R₂ to R₆ are to be substituted with groups other than hydrogen in any one of the compounds represented by formulae (I) and (Ia) and mixtures thereof; and when R₇ is hydrogen, the above compounds of formulae (I) and (Ia) may form inorganic or organic salts, the salt being represented by formula (II) below: ##STR4##

When X is inorganic, it is alkali metals, alkaline earth metals, Co, Ni, Cu, Zn, or Ag.

When the cation X⁺ is organic, X⁺ is represented by formula IIIa

    N.sup.+ R.sub.a R.sub.b R.sub.c R.sub.d                    (IIIa)

wherein R_(a) is hydrogen, C₁ -C₃₀ alkyl straight chain or branched [optionally mono- or disubstituted with HO--, CH₃ O₂ C--, CH₃ S--, C₃ -C₁₈ alkenylaminoalkylene (C₁ -C₃), H₂ N--, (CH₃)₂ N--, ##STR5## C₃ -C₆ alkenyl, C₃ -C₆ alkynyl, C₃ -C₆ cycloalkyl, ##STR6## wherein R_(e) and R_(f) each may be H, CH₃ or n-C₁₆ H₃₃ SO₂ --; R_(b) is hydrogen, C₁ -C₃₀ alkyl straight chain or branched [optionally mono- or disubstituted with HO-- or ##STR7## R_(c) is hydrogen, C₁ -C₃₀ alkyl straight chain or branched [optionally mono- or disubstituted with HO-- or ##STR8## R_(d) is hydrogen, C₁ -C₃₀ alkyl straight chain or branched [optionally substituted with HO--, Cl-- or ##STR9## and when R_(a) and R_(b) are taken together with the nitrogen they are attached to they represent a moiety of ##STR10## wherein R_(c) and R_(d) are defined as above.

The organic cation X⁺ may also be imidazolium, pyridinium, quinolinium, dithiolium, tetrazolium or be represented by formula IIIb ##STR11## wherein R_(g) and R_(h) each are C₁ -C₃ alkyl; R_(j) is hydrogen, halogen, C₁ -C₃ alkyl or C₁ -C₃ alkoxy; R_(i) and R_(k) each are hydrogen C₁ -C₆ alkyl straight chain or branched; C₃ -C₆ cycloalkyl, ##STR12## wherein U and V each are hydrogen, halogen, C₁ -C₃ alkyl, C₁ -C₃ alkoxy, CN or CF₃ ; W is hydrogen or C₁ -C₃ alkyl; and each symbol represents a single or double bond, wherein if both are single bonds then the cations are pyrazolidium cations represented by formula (IIIc) ##STR13## wherein R_(g) to R_(k) are as defined above; and when one of the symbols represents a double bond then the cations are pyrazolinium cations represented by formula (IIId) ##STR14## wherein R_(g) to R_(k) are as defined above; and when both symbols represent double bonds, then the cations are pyrazolium cations represented by formula (IIIe) ##STR15## wherein R_(g) to R_(k) are as defined above.

X may also be represented by Formulae IIIf and IIIg

    R.sub.1 -P.sup.+ (Rm).sub.3                                (IIIf)

wherein R₁ is C₁ -C₆ alkyl, ##STR16## wherein U and V are as hereinabove defined; R_(m) is C₁ -C₆ alkyl or ##STR17## SR_(a) ⁺ R_(b) R_(c) (IIIg); and I⁺ R_(a) R_(b) (IIIh).

A group of compounds represented by formula IV when n is 0, of particular interest for use in the invention, are graphically illustrated and described as follows: ##STR18## wherein R₂ is Br, Cl, F, I, C₁ -C₄ alkyl, OCHF₂, CF₃, SR₈, SO₂ R₈, or COR₉ ; R₄ is Br, Cl, F, I, CH₃, OCF₃, NHCO--CH₃, CN, SR₈, SO₂ R₈, COR₉, phenoxy or substituted phenoxy wherein the substituents are selected from the group described above; R₆ is Br, Cl, F, I or C₁ -C₄ alkyl; R₈ and R₉ are as hereinabove defined; and cation X⁺ is as hereinabove defined.

A second group of compounds represented by formula (IV) above and of interest are those wherein R₂, R₄ and R₆ are each bromine; X⁺ is R_(a) NH₃ ⁺, wherein R_(a) is ##STR19##

A third group of compounds represented by formula IV, above, of interest are those wherein R₂, R₄ and R₆ each are bromine and X⁺ is ##STR20##

A fourth group of compounds represented by formula IV, above are those wherein R₂, R₄ and R₆ each are bromine and X⁺ is ##STR21##

A fifth group of compounds of interest and represented by formula IV above are those wherein R₂, R₄ and R₆ each are bromine and X⁺ is ##STR22##

Another, important group of plant regulating compounds represented by formula II above, are those wherein the cation X⁺ is pyrazolium, pyrazolinium or pyrazolidinium moieties as represented by structural formula IV and discussed and described in detail as follows: ##STR23## comprising a cation of formula (IIIb) ##STR24## wherein R_(g) and R_(h) each are methyl or ethyl; R_(j) is hydrogen, bromine, chlorine, fluorine, methyl or methoxy; R_(i) and R_(k) each are hydrogen, cyclohexyl, ##STR25## U is hydrogen, CF₃, methyl, methoxy, chlorine, bromine or fluorine; and a phenylnitramine anion of formula (IV) ##STR26## wherein R₂, R₄ and R₆ each are bromine, chlorine, iodine, methyl or trifluoromethyl; and represents a single or double bond.

A preferred group of salts useful in the invention are represented by formula (IVa) above are those wherein each of the represent double bonds; R_(g) and R_(h) each are methyl; R_(j) is hydrogen; R_(i) and R_(k) each are cyclohexyl, ##STR27## U is hydrogen, methyl, methoxy, chlorine, fluorine or trifluoromethyl.

The most preferred compounds useful in the invention are represented by formula (IVa) are those, wherein R₂, R₄, R₆ each are trifluoromethyl, bromine or iodine; R_(k) and R_(i) each are phenyl.

Of special interest are formula IV salts represented by the structures shown below: ##STR28##

Other compounds of formula II useful in the invention are compounds wherein the anion has the structure (V) ##STR29## and R₂ and R₆ each are halogen, C₁ -C₄ alkyl or C₁ -C₃ haloalkyl; cation X⁺ is as hereinabove defined. Among the compounds described above, preferred are those wherein R₂ and R₆ each are bromine, chlorine, iodine or CF₃ ; and cation X⁺ is C₁₈ H₃₅ N⁺ H₃ or is the pyrazolium cation of formula ##STR30## wherein R_(h) is C₁ -C₂ alkyl; R_(i) is phenyl; R_(j) is hydrogen, halogen or methyl.

Also useful in the invention are compounds formula II salts wherein the anion is represented by structure (VI) ##STR31## R₂ and R₃ each are halogen or C₁ -C₄ alkyl; cation X⁺ is as hereinabove defined. Of particular interest are those salts wherein R₂ and R₃ each are bromine or chlorine; cation X⁺ is C₁₈ H₃₅ N⁺ H₃ or the pyrazolium cation of formula ##STR32## wherein R_(h) is C₁ -C₂ alkyl; R_(i) is phenyl; R_(j) is hydrogen, halogen or methyl.

Among the trisubstituted salts of formula II useful in the invention the following are of interest: ##STR33## wherein R₂, R₃ and R₆ each are halogen, alkyl C₁ -C₄ or haloalkyl C₁ -C₄ ; cation X⁺ is as hereinabove defined; and especially those wherein R₂, R₃ and R₆ each are Br, Cl or I and when R₂ and R₃ are Cl the R₆ is Br, or if one is CF₃, the other two have to be Br or I; and cation X⁺ is C₁₈ H₃₅ N⁺ H₃ or is the moiety ##STR34## R_(h) is C₁ -C₂ alkyl; R_(i) is phenyl; R_(j) is hydrogen, halogen or methyl.

Further compounds useful in the invention are of the structure: ##STR35## wherein R₂, R₃ and R₅ each are Br, Cl, I, F or C₁ -C₄ alkyl; the cation especially those wherein X⁺ is as hereinabove defined, and is preferably R₂, R₃ and R₅ all are Br or I, and cation X⁺ is C₁₈ H₃₅ N⁺ H₃ or a pyrazolium cation of formula: ##STR36## wherein R_(h) is C₁ -C₂ alkyl; R_(i) is phenyl; R_(j) is hydrogen, halogen or methyl.

A further trisubstituted salt useful in the invention is the structure: ##STR37## wherein R₂, R₃ and R₄ are Br, Cl, I or C₁ -C₂ alkyl; cation X⁺ is as hereinabove defined, preferentially C₁₈ H₃₅ N⁺ H₃ or the moiety ##STR38## wherein R_(h) is C₁ -C₂ alkyl; R_(i) is phenyl; R_(j) is hydrogen, halogen or methyl.

Among the tetrasubstituted salts of formula II useful in the invention are of the formula: ##STR39## wherein R₂ and R₆ each are C₁ -C₄ alkyl, Br, Cl, F or CF₃ ; R₃ is CH₃, CH₃ O, CO₂ CH₃, SO₂ CH₃, NH₂, NHCOCH₃, CN, NO₂, Cl or F; R₄ is C₁ -C₂ alkyl, Br, Cl or F; cation X⁺ is as hereinabove defined. Of particular interest are those compounds wherein substituents R₂ to R₆ are in the combinations given below:

    ______________________________________                                         R.sub.2 R.sub.3          R.sub.4                                                                               R.sub.6                                        ______________________________________                                         CH.sub.3                                                                               Cl               Br     Br                                             Br      Cl               Br     Cl                                             Br      Cl               CH.sub.3                                                                              Br                                             Br      F                Br     Br                                             Br      SO.sub.2 CH.sub.3                                                                               Br     Br                                             Br      NHCOCH.sub.3     Br     Br                                             ______________________________________                                    

and cation X⁺ is C₁₈ H₃₅ N⁺ H₃ or a pyrazolium cation of formula ##STR40## wherein R_(h) is C₁ -C₂ alkyl; R_(i) is phenyl; R_(j) is hydrogen, halogen or methyl.

Among the formula II salts wherein n is 1, the following are useful in the invention: ##STR41## wherein R₁ is hydrogen, C₁ -C₃ alkyl, C₁ -C₃ haloalkyl, CN, halogen, NO₂, SO₂ R₈, COR₉, phenyl or substituted phenyl and the substituents are CH₃, CF₃, CH₃ O, NO₂, Br, Cl, F or OCH₂ CO₂ C₂ H₅ ; R₂, R₃ and R₆ each are hydrogen, C₁ -C₄ alkyl, Br, Cl, F or CF₃ ; R₄ is hydrogen, C₁ -C₂ alkyl, Br, Cl or F; cation X⁺ is as hereinabove defined; but is preferably Na⁺, C₁₈ H₃₅ N⁺ H₃ or a pyrazolium cation of formula ##STR42## wherein R_(h) is C₁ -C₂ alkyl; R_(i) is phenyl; R_(j) is hydrogen, halogen or methyl; R₈ and R₉ are as hereinabove defined.

Among the compounds represented by formula I wherein n is 0 and R₇ is other than hydrogen, the following are of useful in the invention: ##STR43## wherein R₂ and R₆ each are Cl, Br, I, NO₂ ; R₃ is hydrogen or C₁ -C₂ alkyl; R₄ is hydrogen, halogen or C₁ -C₃ alkyl; R₇ is C₁ -C₁₂ alkyl optionally substituted with halogen or CN, C₃ -C₄ alkenyl, C₃ -C₄ alkynyl, (C₁ -C₃ alkyl)₃ SiCH₂ --, the methyl esters of lower alkanoic acids or the moiety ##STR44## wherein o is an integer of 0,1,2 or 3 and the moiety may optionally be substituted with halogen, C₁ -C₂ alkyl, C₁ -C₂ alkoxy or nitro.

Among the compounds of formula Ia wherein n is 0 and R₇ is other than hydrogen the following are useful in the invention: ##STR45## wherein R₂ and R₆ each are Cl, Br, I or NO₂ ; R₃ is hydrogen or C₁ -C₂ alkyl; R₄ is hydrogen, halogen or C₁ -C₃ alkyl; R₇ is C₁ -C₁₂ alkyl optionally substituted with halogen or CN, C₃ -C₄ alkenyl, C₃ -C₄ alkynyl, (C₁ -C₃ alkyl)₃ SiCH₂ --, the methyl esters of lower alkanoic acids or the moiety ##STR46## wherein o is an integer of 0,1,2 or 3 and the moiety may optionally be substituted with halogen, C₁ -C₂ alkyl, C₁ -C₂ alkoxy or NO₂.

Among the compounds of the invention the following compounds represented by formulae (I) and (Ia) are novel: ##STR47## wherein n is an integer of 0 or 1; R₁ is hydrogen, C₁ -C₃ alkyl, C₁ -C₃ haloalkyl, CN, halogen, NO₂, SO₂ R₈, COR₉, phenyl or substituted phenyl and the substituents are CH₃, CF₃, CH₃ O, halogen, NO₂ or OCH₂ CO₂ C₂ H₅ ; R₂ and R₆ are hydrogen, halogen, C₁ -C₄ alkyl, C₁ -C₄ haloalkyl, C₁ -C₄ haloalkoxy, SO₂ R₈, SR₈ or COR₁₀ ; R₃ is hydrogen, C₁ -C₄ alkyl, C₁ -C₄ alkoxy, NH₂, NHCOCH₃, halogen, NO₂, SO₂ R₈, CN or CO₂ CH₃ ; R₄ is hydrogen, halogen, C₁ -C₂ alkyl, SO₂ R₈, COR₉, CN, NHCOCH₃, SO₂ NR₁₀ R₁₁, ##STR48## phenoxy or substituted phenoxy and the substituents are CH₃, CF₃, OCF₃, CH₃ O, halogen, NO₂ or OCH₂ CO₂ C₂ H₅ ; R₅ is hydrogen, C₁ -C₃ alkyl or halogen; R₇ is hydrogen, C₁ -C₁₂ alkyl optionally substituted with halogen or CN, C₃ -C₄ alkenyl, C₃ -C₄ alkynyl, the methyl esters of lower alkanoic acids or the moiety ##STR49## wherein o is an integer of 0,1,2 or 3, and the moiety may optionally be substituted with halogen, C₁ -C₂ alkyl, C₁ -C₂ alkoxy, (C₁ -C₃ alkyl)₃ SiCH₂ -- or NO₂ ; R₈ is C₁ -C₆ alkyl, phenyl or benzyl; R₉ is hydrogen, hydroxyl, C₁ -C₃ alkyl, C₁ -C₃ alkoxy or phenyl; R₁₀ and R₁₁ each are hydrogen, C₁ -C₄ alkyl or phenyl; with the proviso that not less than two and not more than four of R₂ to R₆ are to be substituted with groups other than hydrogen in any one of the compounds of formulae I and Ia and mixtures thereof; and with the additional proviso that when R₁, R₅ and R₇ are hydrogen and n is 0 then:

a if only R₂ and R₃ are substituted, they cannot be both CH₃ or Cl or combinations thereof;

b if only R₂ and R₆ are substituted they cannot be both CH₃, C₂ H₅, C₃ H₇, Br or Cl or combinations thereof;

c if R₂, R₄ and R₆ are substituted they cannot be all Br, Cl, CH₃ or combinations thereof and if R₂ and R₆ are both Br then R₄ cannot be CN;

d if R₃ is NO₂ then R₂, R₄ and R₆ cannot be all Br.

A group of novel compounds represented by formula Ib, and of particular interest are graphically illustrated and described as follows: ##STR50## wherein R₂ is Br, Cl, F, I, C₁ -C₄ alkyl, OCHF₂, CF₃, SR₈, SO₂ R₈ or COR₉ ; R₄ is Br, Cl, F, I, CH₃, OCF₃, NHCOCH₃, CN, SR₈, SO₂ R₈, COR₉, phenoxy or substituted phenoxy wherein the substituents are CH₃, CF₃, CH₃ O, halogen, NO₂ or OCH₂ CO₂ C₂ H₅ ; R₆ is Br, Cl, F, I or C₁ -C₄ alkyl; R₈ is C₁ -C₆ alkyl, phenyl or benzyl; R₉ is hydrogen, hydroxyl, C₁ -C₃ alkyl, C₁ -C₃ alkoxy or phenyl; with the proviso that R₂, R₄ and R₆ cannot be all Br, Cl, CH₃ or combinations thereof and with the further proviso that if R₂ and R₆ are both Br then R₄ cannot be CN.

Another group of novel compounds represented by formula Ic and of interest are illustrated and described as follows: ##STR51## wherein R₂ and R₆ each are Br, Cl, F, I, C₁ -C₄ alkyl, C₁ -C₄ haloalkyl, C₁ -C₄ haloalkoxy, SR₈, SO₂ R₈ or COR₁₀ ; R₈ is C₁ -C₆ alkyl, phenyl or benzyl; R₁₀ is hydrogen, C₁ -C₄ alkyl or phenyl; with the proviso that R₂ and R₆ cannot be both CH₃, C₂ H₅, C₃ H₇, Br or Cl or combinations thereof.

The following group of novel compounds of formula (Id) and of interest are graphically illustrated and described as follows: ##STR52## wherein R₂ is Br, Cl, F, I, C₁ -C₄ alkyl, C₁ -C₄ haloalkyl, C₁ -C₄ haloalkoxy, SR₈, SO₂ R₈ or COR₁₀ ; R₃ is Br, Cl, F, I, C₁ -C₄ alkyl, C₁ -C₄ alkoxy, NH₂, NHCOCH₃, NO₂, SO₂ R₈, CN or CO₂ CH₃ ; R₈ is C₁ -C₆ alkyl, phenyl or benzyl; R₁₀ is hydrogen, C₁ -C₄ alkyl or phenyl; with the proviso that R₂ and R₃ cannot be both CH₃ or Cl or combinations thereof.

Another group of novel compounds of formula (Ie) and of interest are graphically illustrated and described as follows: ##STR53## wherein R₂ and R₆ are Br, Cl, F, I, C₁ -C₄ alkyl, C₁ -C₄ haloalkyl, C₁ -C₄ haloalkoxy, SO₂ R₈, SR₈ or COR₁₀ ; R₃ is Br, Cl, F, I, C₁ -C₄ alkyl, C₁ -C₄ alkoxy, NH₂, NHCOCH₃, NO₂, SO₂ R₈, CN or CO₂ CH₃ ; R₈ is C₁ -C₆ alkyl, phenyl or benzyl, R₁₀ is hydrogen, C₁ -C₄ alkyl or phenyl.

A group of novel compounds represented by formula If and useful in the invention are graphically illustrated and described as follows: ##STR54## wherein R₂ is Br, Cl, F, I, C₁ -C₄ alkyl, C₁ -C₄ haloalkyl, C₁ -C₄ haloalkoxy, SR₈, SO₂ R₈ or COR₁₀ ; R₃ is Br, Cl, F, I, C₁ -C₄ alkyl, C₁ -C₄ alkoxy, NH₂, NHCOCH₃, NO₂, SO₂ R₈, CN or CO₂ CH₃ ; R₅ is Br, Cl, F, I, or C₁ -C₃ alkyl; R₈ is C₁ -C₆ alkyl, phenyl or benzyl; R₁₀ is hydrogen, C₁ -C₄ alkyl or phenyl.

Still another group of novel compounds represented by formula Ig, and of interest are graphically illustrated and described as follows: ##STR55## wherein R₂ is Br, Cl, F, I, C₁ -C₄ alkyl, C₁ -C₄ haloalkyl, C₁ -C₄ haloalkoxy, SO₂ R₈, SR₈ or COR₁₀ ; R₃ is Br, Cl, F, I, C₁ -C₄ alkyl, C₁ -C₄ alkoxy, NH₂, NHCOCH₃, NO₂, SO₂ R₈, CN or CO₂ CH₃ ; R₄ is Br, Cl, F, I, C₁ -C₂ alkyl, SO₂ R₈, COR₉, CN, NHCOCH₃, SO₂ NR₁₀ R₁₁, ##STR56## phenoxy or substituted phenoxy and the substituents are CH₃, CF₃, CH₃ O, Br, Cl, F, I, NO₂ or OCH₂ CO₂ C₂ H₅ ; R₈ is C₁ -C₆ alkyl, phenyl or benzyl; R₉ is hydrogen, hydroxyl, C₁ -C₃ alkyl, C₁ -C₃ alkoxy or phenyl; R₁₀ and R₁₁ each are hydrogen, C₁ -C₄ alkyl or phenyl.

A group of novel compounds represented by formula Ih and useful in the invention are graphically illustrated and described as follows: ##STR57## wherein R₂ and R₆ are Br, Cl, F, I, C₁ -C₄ alkyl, C₁ -C₄ haloalkyl, C₁ -C₄ haloalkoxy, SO₂ R₈, SR₈ or COR₁₀ ; R₃ is C₁ -C₄ alkyl, C₁ -C₄ alkoxy, NH₂, NHCOCH₃, Br, Cl, F, I, NO₂, SO₂ R₈, CN or CO₂ CH₃ ; R₄ is Br, Cl, F, I, C₁ -C₂ alkyl, SO₂ R₈, COR₉, CN, NHCOCH₃, SO₂ NR₁₀ R₁₁, ##STR58## phenoxy or substituted phenoxy and the substituents are CH₃, CF₃, CH₃ O, Br, Cl, F, I, NO₂ or OCH₂ CO₂ --C₂ H₅ ; R₈ is C₁ -C₆ alkyl, phenyl or benzyl; R₉ is hydrogen, hydroxyl, C₁ -C₃ alkyl, C₁ -C₃ alkoxy or phenyl; R₁₀ and R₁₁ are hydrogen, C₁ -C₄ alkyl or phenyl; with the proviso that when R₃ is NO₂, then R₂, R₄ and R₆ cannot be all Br.

A group of novel compounds represented by formula Ii and of interest are graphically illustrated and described as follows: ##STR59## wherein R₁ is hydrogen, C₁ -C₃ alkyl, C₁ -C₃ haloalkyl, CN, Br, Cl, F, I, NO₂, SO₂ R₈, COR₉, phenyl or substituted phenyl and the substituents are CH₃, CF₃, CH₃ O, NO₂ or OCH₂ CO₂ C₂ H₅ ; R₂ and R₆ are hydrogen, Br, Cl, F, I, C₁ -C₄ alkyl, C₁ -C₄ haloalkyl, C₁ -C₄ haloalkoxy, SO₂ R₈, SR₈ or COR₁₀ ; R₃ is hydrogen, C₁ -C₄ alkyl, C₁ -C₄ alkoxy, NH₂, NHCOCH₃, Br, Cl, F, I, NO₂, SO₂ R₈, CN or CO₂ CH₃ ; R₄ is hydrogen, Br, Cl, F, I, C₁ -C₂ alkyl, SO₂ R₈, COR₉, CN, NHCOCH₃, SO₂ NR₁₀ R₁₁, ##STR60## phenoxy or substituted phenoxy and the substituents are CH₃, CF₃, CH₃ O, Br, Cl, F, I, NO₂ or OCH₂ CO₂ C₂ H₅ ; R₈ is C₁ -C₆ alkyl, phenyl or benzyl; R₉ is hydrogen, hydroxyl, C₁ -C₃ alkyl, C₁ -C₃ alkoxy or phenyl; R₁₀ and R₁₁ are hydrogen, C₁ -C₄ alkyl or phenyl; with the proviso that not less than two of R₂ to R₆ are to be substituted with groups other than hydrogen.

Still another group of novel compounds of formula Ij useful in the invention are graphically illustrated and described as follows: ##STR61## wherein R₂ and R₃ are hydrogen, Br, Cl, F, I, C₁ -C₄ alkyl, C₁ -C₄ haloalkyl, C₁ -C₄ haloalkoxy, SO₂ R₈, SR₈, or COR₁₀ ; R₃ is hydrogen, C₁ -C₄ alkyl, C₁ -C₄ alkoxy, NH₂, NHCOCH₃, Br, Cl, F, I, NO₂, SO₂ R₈, CN or CO₂ CH₃ ; R₄ is hydrogen, Br, Cl, F, I, C₁ -C₂ alkyl, SO₂ R₈, COR₉, CN, NHCOCH₃, SO₂ NR₁₀ R₁₁, ##STR62## phenoxy or substituted phenoxy and the substituents are CH₃, CF₃, CH₃ O, Br, Cl, F, I, NO₂ or OCH₂ CO₂ C₂ H₅ ; R₇ is C₁ -C₁₂ alkyl optionally substituted with halogen or CN, C₃ -C₄ alkenyl, C₃ -C₄ alkynyl, the methyl esters of lower alkanoic acids or the moiety ##STR63## wherein o is an integer of 0,1,2 or 3, and the moiety may optionally be substituted with Br, Cl, F, I, C₁ -C₂ alkyl, C₁ -C₂ alkoxy, (C₁ -C₃ alkyl)₃ SiCH₂ --, or NO₂ ; R₈ is C₁ -C₆ alkyl, phenyl or benzyl; R₉ is hydrogen, hydroxyl, C₁ -C₃ alkyl, C₁ -C₃ alkoxy or phenyl; R₁₀ and R₁₁ are hydrogen, C₁ -C₄ alkyl or phenyl; with the provisos that when; a R₂, R₄ and R₆ are Br then R₇ cannot be CH₃ ; b and when R₂ and R₆ are both Br then R₇ cannot be C₁ -CHd 4 alkyl, and o cannot be an integer of 1,2 or 3; c and when R₂ and R₆ are both CH₃ then o cannot be 3.

The novel group of compounds represented by formula Ik and of particular interest are graphically illustrated and described as follows: ##STR64## wherein R₂ and R₆ are hydrogen, Br, Cl, F, I, C₁ -C₄ alkyl, C₁ -C₄ haloalkyl, C₁ -C₄ haloalkoxy, SO₂ R₈, SR₈ or COR₁₀ ; R₃ is hydrogen, C₁ -C₄ alkyl, C₁ -C₄ alkoxy, NH₂,NHCOCH₃, Br, Cl, F, I, NO₂, SO₂ R₈, CN or COCH₃ ; R₄ is hydrogen, Br, Cl, F, I, C₁ -C₂ alkyl, SO₂ R₈, COR₉, CN, NHCOCH₃, SO₂ NR₁₀ R₁₁, ##STR65## phenoxy or substituted phenoxy and the substituents are CH₃, CF₃, CH₃ O, Br, Cl, F, I, NO₂ or OCH₂ CO₂ C₂ H₅ ; R₇ is C₁ -C₁₂ alkyl optionally substituted with halogen or CN, C₃ -C₄ alkenyl, C₃ -C₄ alkynyl, the methyl esters of lower alkanoic acids or the moiety ##STR66## wherein o is an integer of 0,1,2 or 3, and the moiety may optionally be substituted with Br, Cl, F, I, C₁ -C₂ alkyl, C₁ -C₂ alkoxy, (C₁ -C₃ alkyl)₃ SiCH₂ -- or NO₂ ; R₈ is C₁ -C₆ alkyl; phenyl or benzyl; R₉ is hydrogen, hydroxyl, C₁ -C₃ alkyl, C₁ -C₃ alkoxy or phenyl; R₁₀ and R₁₁ are hydrogen, C₁ -C₄ alkyl or phenyl.

The hereinabove identified compounds of formulae I and Ia may also form a group of novel inorganic and organic salts represented by formula II and useful in the invention, graphically illustrated and described as follows: ##STR67## wherein n is an integer of 0 or 1; R₁ is hydrogen, C₁ -C₃ alkyl, C₁ -C₃ haloalkyl, CN, Br, Cl, F, I, NO₂, SO₂ R₈, COR₉, phenyl or substituted phenyl and the substituents are CH₃, CF₃, CH₃ O, Br, Cl, F, I, NO₂ or OCH₂ CO₂ C₂ H₅ ; R₂ and R₆ are hydrogen, halogen, C₁ -C₄ alkyl, C₁ -C₄ haloalkyl, C₁ -C₄ haloalkoxy, SO₂ R₈, SR₈ or COR₁₀ ; R₃ is hydrogen, C₁ -C₄ alkyl, C₁ -C₄ alkoxy, NH₂, NHCOCH₃, Br, Cl, F, I, NO₂, SO₂ R₈, CN or CO₂ CH₃ ; R₄ is hydrogen, Br, Cl, F, I, C₁ -C₂ alkyl, SO₂ R₈, COR₉, CN, NHCOCH₃, SO.sub. 2 NR₁₀ R₁₁, OCF₃, ##STR68## phenoxy or substituted phenoxy and the substituents are CH₃, CF₃, CH₃ O, Br, Cl, F, I, NO₂ or OCH₂ CO₂ C₂ H₅ ; R₅ is hydrogen, C₁ -C₃ alkyl, Br, Cl, F, or I; X⁺ is inorganic or organic;

when X is inorganic, it is alkali metals, alkaline earth metals, Co, Zn, or Ag;

when the cation X⁺ is organic, X⁺ is represented by formula IIIa

    N.sup.+ R.sub.a R.sub.b R.sub.c R.sub.d                    (IIIa)

wherein R_(a) is hydrogen, C₁ -C₃₀ alkyl straight chain or branched [optionally mono- or disubstituted with HO--, CH₃ O₂ C--, CH₃ S--, C₃ -C₁₈ alkenylaminoalkylene (C₁ -C₃), H₂ N, (CH₃)₂ N--, ##STR69## C₃ -C₆ alkenyl, C₃ -C₆ alkynyl, C₃ -C₆ cycloalkyl, ##STR70## wherein R_(e) and R_(f) each may be H, CH₃ or n-C₁₆ H₃₃ SO₂ --; R_(b) is hydrogen, C₁ -C₃₀ alkyl straight chain or branched [optionally mono- or disubstituted with HO-- or ##STR71## R_(c) is hydrogen, C₁ -C₃₀ alkyl straight chain or branched [optionally mono- or disubstituted with HO-- or ##STR72## R_(d) is hydrogen, C₁ -C₃₀ alkyl straight chain or branched [optionally substituted with HO--, CL-- or ##STR73## and when R_(a) and R_(b) are taken together with the nitrogen they are attached to they represent a moiety of ##STR74## wherein R_(c) and R_(d) are defined as above;

organic cation X⁺ may also be imidazolium, pyridinium, quinolinium, dithiolium, tetrazolium or be represented by formula IIIb ##STR75## wherein R_(g) and R_(h) each are C₁ -C₃ alkyl; R_(j) is hydrogen, halogen, C₁ -C₃ alkyl or C₁ -C₃ alkoxy; R_(i) and R_(k) each are hydrogen C₁ -C₆ alkyl straight chain or branched, C₃ -C₆ cycloalkyl, ##STR76## wherein U and V each are hydrogen, halogen, C₁ -C₃ alkyl, C₁ -C₃ alkoxy, CN or CF₃ ; W is hydrogen or C₁ -C₃ alkyl; and each symbol represents a single or double bond, wherein if both are single bonds then the cations are pyrazolidinium cations represented by formula IIIc ##STR77## wherein R_(g) and R_(k) are as defined above; and

X⁺ may also be represented by formulae IIIf and IIIg

    R.sub.1 -P.sup.+ (Rm).sub.3                                IIIf

wherein R₁ is C₁ -C₆ alkyl, ##STR78## wherein U and V are as hereinabove defined; R_(m) is C₁ -C₆ alkyl or ##STR79## S⁺ R_(a) R_(b) R_(c) (IIIg) and I⁺ R_(a) R_(b) (IIIh), wherein R_(a), R_(b) and R_(c) are as hereinabove defined; with the proviso that not less than two of R₂ to R₆ are to be substituted with groups other than hydrogen in any one of the compounds of formula II.

A group of novel salts represented by formulae II, IV and IVa in the disclosure and of special interest are graphically illustrated and described as follows: ##STR80## R₂ is Br, Cl, F, I, C₁ -C₄ alkyl, OCHF₂, CF₃, SR₈, SO₂ R₈ or COR₉ ; R₄ is Br, Cl, F, I, CH₃, OCF₃, NHCOCH₃, CN, SR₈, SO₂ R₈, COR₉, phenoxy or substituted phenoxy and the substituents are CH₃, CF₃, OCH₃, Br, Cl, F, I or C₁ -C₄ alkyl; R₆ is Br, Cl, F, I or C₁ -C₄ alkyl; R₈ is C₁ -C₆ alkyl, phenyl or benzyl; R₉ is hydrogen, hydroxyl, C₁ -C₃ alkyl, C₁ -C₃ alkoxy or phenyl; and cation X⁺ is inorganic or organic,

when X is inorganic, it is alkali metals, alkaline earth metals, Co, Zn, or Ag;

when the cation X⁺ is organic, X⁺ is represented by formula IIIa

    N.sup.+ R.sub.a R.sub.b R.sub.c R.sub.d                    (IIIa)

wherein R_(a) is hydrogen, C₁ -C₃₀ alkyl straight chain or branched [optionally mono- or disubstituted with HO--, CH₃ O₂ C--, CH₃ S--, C₃ -C₁₈ alkenylaminoalkylene (C₁ -C₃), H₂ N, (CH₃)₂ N--, ##STR81## C₃ -C₆ alkenyl, C₃ -C₆ alkynyl, C₃ -C₆ cyloalkyl, ##STR82## wherein R_(e) and R_(f) each may be H, CH₃ or n--C₁₆ H₃₃ SO₂ --; R_(b) is hydrogen, C₁ -C₃₀ alkyl straight chain or branched [optionally mono- or disubstituted with HO-- or ##STR83## R_(c) is hydrogen, C₁ 14 C₃₀ alkyl straight chain or branched [optionally mono- or disubstituted with HO-- or ##STR84## R_(d) is hydrogen, C₁ -C₃₀ alkyl straight chain or branched [optionally substituted with HO--, Cl-- or ##STR85## and when R_(a) and R_(b) are taken together with the nitrogen they are attached to they represent a moiety of ##STR86## wherein R_(c) and R_(d) are defined as above;

organic cation X⁺ may also be imidazolium, pyridinium, quinolinium, dithiolium, tetrazolium or be represented by formula IIIb ##STR87## wherein R_(g) and R_(h) each are C₁ -C₃ alkyl; R_(j) is hydrogen, halogen, C₁ -C₃ alkyl or C₁ -C₃ alkoxy; R_(i) and R_(k) each are hydrogen C₁ -C₆ alkyl straight chain or branched, C₃ -C₆ cycloalkyl, ##STR88## wherein U and V each are hydrogen, halogen, C₁ -C₃ alkyl, C₁ -C₃ alkoxy, CN or CF₃ ; W is hydrogen or C₁ -C₃ alkyl; and each symbol represents a single or double bond, wherein if both are single bonds then the cations are pyrazolidinium cations represented by formula IIIc ##STR89## wherein R_(g) and R_(k) are as defined above; and

X⁺ may also be represented by formulae IIIf and IIIg

    R.sub.1 -P.sup.+ (Rm).sub.3                                IIIf

wherein R₁ is C₁ -C₆ alkyl, ##STR90## wherein U and V are as hereinabove defined; R_(m) is C₁ -C₆ alkyl or ##STR91## S⁺ R_(a) R_(b) R_(c) (IIIg) and I⁺ R_(a) R_(b) (IIIh), wherein R_(a),R_(b) and R_(c) are as hereinabove defined; with the provisos that when R₂, R₄ and R₆ each are Br, Cl or at least one of them is CH₃, cation X⁺ cannot be Ba²⁺ ; and when R₂, R₄ and R₆ are Br, Cl or mixtures thereof, X⁺ cannot be Na⁺ ; and when R₂, R₄ and R₆ each are Br, X⁺ cannot be K⁺, Ag⁺, NH₄ ⁺ or anilino.

Another group of novel salts represented by formula V are of interest and are graphically illustrated and described as follows: ##STR92## wherein R₂ and R₆ each are Br, Cl, F, I, C₁ -C₄ alkyl, C₁ -C₄ haloalkyl, C₁ -C₄ haloalkoxy, SR₈, SO₂ R₈ or COR₁₀ ; R₈ is C₁ -C₆ alkyl, phenyl or benzyl; R₁₀ is hydrogen, C₁ -C₄ alkyl or phenyl; X is inorganic or organic,

when X is inorganic, it is alkali metals, alkaline earth metals, Co, Zn, or Ag;

when the cation X⁺ is organic, X⁺ is represented by formula IIIa

    N.sup.+ R.sub.a R.sub.b R.sub.c R.sub.d                    (IIIa)

wherein R_(a) is hydrogen, C₁ -C₃₀ alkyl straight chain or branched [optionally mono- or disubstituted with HO--, CH₃ O₂ C--, CH₃ S--, C₃ -C₁₈ alkenylaminoalkylene (C₁ -C₃), H₂ N, (CH₃)₂ N--, ##STR93## C₃ -C₆ alkenyl, C₃ -C₆ alkenyl, C₃ -C₆ cycloalkyl, ##STR94## wherein R_(e) and R_(f) each may be H, CH₃ or n-C₁₆ H₃₃ SO₂ --; R_(b) is hydrogen, C₁ -C₃₀ alkyl straight chain or branched [optionally mono- or disubstituted with HO-- or ##STR95## R_(c) is hydrogen, C₁ -C₃₀ alkyl straight chain or branched [optionally mono- or disubstituted with HO-- or ##STR96## R_(d) is hydrogen, C₁ -C₃₀ alkyl straight chain or branched [optionally substituted with HO--, Cl-- or ##STR97## and when R_(a) and R_(b) are taken together with the nitrogen they are attached to they represent a moiety of ##STR98## wherein R_(c) and R_(d) are defined as above;

organic cation X⁺ may also be imidazolium, pyridinium, quinolinium, dithiolium, tetrazolium or be represented by formula IIIb ##STR99## wherein R_(g) and R_(h) each are C₁ -C₃ alkyl; R_(j) is hydrogen, halogen, C₁ -C₃ alkyl or C₁ -C₃ alkoxy; R_(i) and R_(k) each are hydrogen C₁ -C₆ alkyl straight chain or branched, C₃ -C₆ cycloalkyl, ##STR100## wherein U and V each are hydrogen, halogen, C₁ -C₃ alkyl, C₁ -C₃ alkoxy, CN or CF₃ ; W is hydrogen or C₁ -C₃ alkyl; and each symbol represents a single or double bond, wherein if both are single bonds then the cations are pyrazolidinium cations represented by formula IIIc ##STR101## wherein R_(g) to R_(k) are as defined above; and

X⁺ may also be represented by formulae IIIf and IIIg

    R.sub.1 -P.sup.+ (Rm).sub.3                                IIIf

wherein R₁ is C₁ -C₆ alkyl, ##STR102## wherein U and V are as hereinabove defined; Rm is C₁ -C₆ alkyl or ##STR103## S⁺ -R_(a) R_(b) R_(c) (IIIg) and I⁺ -R_(a) R_(b) (IIIh), wherein R_(a), R_(b) and R_(c) are as hereinabove defined; and with the proviso that when R₂ and R₆ both are Br, then X⁺ cannot be Na⁺, K⁺, Li⁺, Ba⁺⁺, Sr⁺⁺, or NH₄ ⁺.

The following group of novel salts of formula (VI) and of interest are graphically illustrated and described as follows: ##STR104## wherein R₂ is Br, Cl, F, I, C₁ -C₄ alkyl, C₁ -C₄ haloalkyl, C₁ -C₄ haloalkoxy, SR₈, SO₂ R₈ or COR₁₀ ; R₃ is Br, Cl, F, I, C₁ -C₄ alkyl, C₁ -C₄ alkoxy, NH₂, NHCOCH₃, NO₂, SO₂ R₈, CN or CO₂ CH₃ ; R₈ is C₁ -C₆ alkyl, phenyl or benzyl; R₁₀ is hydrogen, C₁ -C₄ alkyl or phenyl; X⁺ is inorganic or organic,

when X is inorganic, it is alkali metals, alkaline earth metals, Co, Zn, or Ag;

when the cation X⁺ is organic, X⁺ is represented by formula IIIa

    N.sup.+ R.sub.a R.sub.b R.sub.c R.sub.d                    (IIIa)

wherein R_(a) is hydrogen, C₁ -C₃₀ alkyl straight chain or branched [optionally mono- or disubstituted with HO--, CH₃ O₂ C--, CH₃ S--, C₃ -C₁₈ alkenylaminoalkylene (C₁ -C₃), H₂ N, (CH₃)₂ N--, ##STR105## C₃ -C₆ alkenyl, C₃ -C₆ alkynyl, C₃ -C₆ cycloalkyl, ##STR106## wherein R_(e) and R_(f) each may be H, CH₃ or n--C₁₆ H₃₃ SO₂ --; R_(b) is hydrogen, C₁ -C₃₀ alkyl straight chain or branched [optionally mono- or disubstituted with HO-- or ##STR107## R_(c) is hydrogen, C₁ -C₃₀ alkyl straight chain or branched [optionally mono- or disubstituted with HO-- or ##STR108## R_(d) is hydrogen, C₁ -C₃₀ alkyl straight chain or branched [optionally substituted with HO--, Cl-- or ##STR109## and when R_(a) and R_(b) are taken together with the nitrogen they are attached to they represent a moiety of ##STR110## wherein R_(c) and R_(d) are defined as above;

organic cation X⁺ may also be imidazolium, pyridinium, quinolinium, dithiolium, tetrazolium or be represented by formula IIIb ##STR111## wherein R_(g) and R_(h) each are C₁ -C₃ alkyl; R_(j) is hydrogen, halogen, C₁ -C₃ alkyl or C₁ -C₃ alkoxy; R_(i) and R_(k) each are hydrogen C₁ -C₆ alkyl straight chain or branched, C₃ -C₆ cycloalkyl, ##STR112## wherein U and V each are hydrogen, halogen, C₁ -C₃ alkyl, C₁ -C₃ alkoxy, CN or CF₃ ; W is hydrogen or C₁ -C₃ alkyl; and each symbol represents a single or double bond, wherein if both are single bonds then the cations are pyrazolidinium cations represented by formula IIIc ##STR113## wherein R_(g) to R_(k) are as defined above, and

X⁺ may also be represented by formulae IIIf and IIIg

    R.sub.1 -P.sup.+ (Rm).sub.3                                IIIf

wherein R₁ is C₁ -C₆ alkyl, ##STR114## wherein U and V are as hereinabove defined; Rm is C₁ -C₆ alkyl or ##STR115## S⁺ R_(a) R_(b) R_(c) (IIIg) and I⁺ R_(a) R_(b) (IIIh), wherein R_(a), R_(b) and R_(c) are as hereinabove defined; and with the proviso that when R₂ and R₃ are both CH₃, X⁺ cannot be Li⁺.

A group of novel salts represented by formula VII and useful in the invention are graphically illustrated and described as follows: ##STR116## wherein R₂ and R₆ each are Br, Cl, F, I, C₁ -C₄ alkyl, C₁ -C₄ haloalkyl, C₁ -C₄ haloalkoxy, SR₈, SO₂ R₈ or COR₁₀ ; R₃ is Br, Cl, F, I, C₁ -C₄ alkyl, C₁ -C₄ alkoxy, NH₂, NHCOCH₃, NO₂, SO₂ R₈, CN or CO₂ CH₃ ; R₈ is C₁ -C₆ alkyl, phenyl or benzyl; R₁₀ is hydrogen, C₁ -C₄ alkyl or phenyl; X⁺ is inorganic or organic,

when X is inorganic, it is alkali metals, alkaline earth metals, Co, Zn, or Ag;

when the cation X⁺ is organic, X⁺ is represented by formula IIIa

    N.sup.+ R.sub.a R.sub.b R.sub.c R.sub.d                    ((IIIa)

wherein R_(a) is hydrogen, C₁ -C₃₀ alkyl straight chain or branched [optionally mono- or disubstituted with HO--, CH₃ O₂ C--, CH₃ S--, C₃ -C₁₈ alkenylaminoalkylene (C₁ -C₃), H₂ N, (CH₃)₂ N--, ##STR117## C₃ -C₆ alkenyl, C₃ -C₆ alkynyl, C₃ -C₆ cycloalkyl, ##STR118## wherein R_(e) and R_(f) each may be H, CH₃ or n--C₁₆ H₃₃ SO₂ --; R_(b) is hydrogen, C₁ -C₃₀ alkyl straight chain or branched [optionally mono- or disubstituted with HO-- or ##STR119## R_(c) is hydrogen, C₁ -C₃₀ alkyl straight chain or branched [optionally mono- or disubstituted with HO-- or ##STR120## R_(d) is hydrogen, C₁ -C₃₀ alkyl straight chain or branched [optionally substituted with HO--, Cl-- or ##STR121## and when R_(a) and R_(b) are taken together with the nitrogen they are attached to they represent a moiety of ##STR122## wherein R_(c) and R_(d) are defined as above;

organic cation X⁺ may also be imidazolium, pyridinium, quinolinium, dithiolium, tetrazolium or be represented by formula IIIb ##STR123## wherein R_(g) and R_(h) each are C₁ -C₃ alkyl; R_(j) is hydrogen, halogen, C₁ -C₃ alkyl or C₁ -C₃ alkoxy; R_(i) and R_(k) each are hydrogen C₁ -C₆ alkyl straight chain or branched, C₃ -C₆ cycloalkyl, ##STR124## wherein U and V each are hydrogen, halogen, C₁ -C₃ alkyl, C₁ -C₃ alkoxy, CN or CF₃ ; W is hydrogen or C₁ -C₃ alkyl; and each symbol represents a single or double bond, wherein if both are single bonds then the cations are pyrazolidinium cations represented by formula IIIc ##STR125## wherein R_(g) to R_(k) are as defined above, and

X⁺ may also be represented by formulae IIIf and IIIg

    R.sub.1 -P.sup.+ (Rm).sub.3                                IIIf

wherein R₁ is C₁ -C₆ alkyl, ##STR126## wherein U and V are as hereinabove defined, Rm is C₁ -C₆ alkyl or ##STR127## S⁺ R_(a) R_(b) R_(c) (IIIg) and I⁺ R_(a) R_(b) (IIIh), wherein R_(a), R_(b) and R_(c) are as hereinabove defined.

A group of novel salts represented by formula VIII and useful in the invention are graphically illustrated and described as follows: ##STR128## wherein R₂ is Br, Cl, F, I, C₁ -C₄ alkyl, C₁ -C₄ haloalkyl, C₁ -C₄ haloalkoxy, SR₈, SO₂ R₈ or COR₁₀ ; R₃ is Br, Cl, F, I, C₁ -C₄ alkyl, C₁ -C₄ alkoxy, NH₂, NHCOCH₃, NO₂, SO₂ R₈, CN or CO₂ CH₃ ; R₅ is Br, Cl, F, I or C₁ -C₃ alkyl; R₈ is C₁ -C₆ alkyl, phenyl or benzyl; R₁₀ is hydrogen, C₁ -C₄ alkyl or phenyl; X⁺ is inorganic or organic,

when X is inorganic, it is alkali metals, alkaline earth metals, Co, Zn, or Ag;

when the cation X⁺ is organic, X⁺ is represented by formula IIIa

    N.sup.+ R.sub.a R.sub.b R.sub.c R.sub.d                    (IIIa)

wherein R_(a) is hydrogen, C₁ -C₃₀ alkyl straight chain or branched [optionally mono- or disubstituted with HO--, CH₃ O₂ C--, CH₃ S--, C₃ -C₁₈ alkenylaminoalkylene (C₁ -C₃), H₂ N, (CH₃)₂ N--, ##STR129## C₃ -C₆ alkenyl, C₃ -C₆ alkynyl, C₃ -C₆ cycloalkyl, ##STR130## wherein R_(e) and R_(f) each may be H, CH₃ or n--C₁₆ H₃₃ SO₂ --; R_(b) is hydrogen, C₁ -C₃₀ alkyl straight chain or branched [optionally mono- or disubstituted with HO-- or ##STR131## R_(c) is hydrogen, C₁ -C₃₀ alkyl straight chain or branched [optionally mono- or disubstituted with HO-- or ##STR132## R_(d) is hydrogen, C₁ -C₃₀ alkyl straight chain or branched [optionally substituted with HO--, Cl-- or ##STR133## and when R_(a) and R_(b) are taken together with the nitrogen they are attached to they represent a moiety of ##STR134## wherein R_(c) and R_(d) are defined as above;

organic cation X⁺ may also be imidazolium, pyridinium, quinolinium, dithiolium, tetrazolium or be represented by formula IIIb ##STR135## wherein R_(g) and R_(h) each are C₁ -C₃ alkyl; R_(j) is hydrogen, halogen, C₁ -C₃ alkyl or C₁ -C₃ alkoxy; R_(i) and R_(k) each are hydrogen C₁ -C₆ alkyl straight chain or branched, C₃ -C₆ cycloalkyl, ##STR136## wherein U and V each are hydrogen, halogen, C₁ -C₃ alkyl, C₁ -C₃ alkoxy, CN or CF₃ ; W is hydrogen or C₁ -C₃ alkyl; and each symbol represents a single or double bond, wherein if both are single bonds then the cations are pyrazolidinium cations represented by formula IIIc ##STR137## wherein R_(g) to R_(k) are as defined above, and

X⁺ may also be represented by formulae IIIf and IIIg

    R.sub.1 -P.sup.+ (RM).sub.3                                IIIf

wherein R₁ is C₁ -C₆ alkyl, ##STR138## wherein U and V are as hereinabove defined; Rm is C₁ -C₆ alkyl or ##STR139## S⁺ R_(a) R_(b) R_(c) (IIIg) and I⁺ R_(a) R_(b) (IIIh), wherein R_(a), R_(b) and R_(c) are as hereinabove defined.

Another group of novel salts represented by formula IX and useful in the invention are graphically illustrated and described as follows: ##STR140## wherein R₂ is Br, Cl, F, I, C₁ -C₄ alkyl, C₁ -C₄ haloalkyl, C₁ -C₄ haloalkoxy, SR₈, SO₂ R₈ pr COR₁₀ ; R₃ is Br, Cl, F, I, C₁ -C₄ alkyl, C₁ -C₄ alkoxy, NH₂, NHCOCH₃, NO₂, SO₂ R₈, CN or CO₂ CH₃ ; R₄ is Br, Cl, F, I, C₁ -C₂ alkyl, SO₂ NR₁₀ R₁₁, NHCOCH₃, CN, SR₈, SO₂ R₈, COR₉, ##STR141## phenoxy or substituted phenoxy and the substituents are CH₃, CF₃, OCH₃, Br, Cl, F, I, NO₂ or OCH₂ CO₂ C₂ H₅ ; R₈ is C₁ -C₆ alkyl, phenyl or benzyl; R₉ is hydrogen, hydroxyl, C₁ -C₃ alkyl, C₁ -C₃ alkoxy or phenyl; R₁₀ and R₁₁ each are hydrogen, C₁ -C₄ alkyl or phenyl; X⁺ is inorganic or organic,

when X is inorganic, it is alkali metals, alkaline earth metals, Co, Zn, or Ag;

when the cation X⁺ is organic, X⁺ is represented by formula IIIa

    N.sup.+ R.sub.a R.sub.b R.sub.c R.sub.d                    (IIIa)

wherein R_(a) is hydrogen, C₁ -C₃₀ alkyl straight chain or branched [optionally mono- or disubstituted with HO--, CH₃ O₂ C--, CH₃ S--, C₃ -C₁₈ alkenylaminoalkylene (C₁ -C₃), H₂ N, (CH₃)₂ N--, ##STR142## C₃ -C₆ alkenyl, C₃ -C₆ alkynyl, C₃ -C₆ cycloalkyl, ##STR143## wherein R_(e) and R_(f) each may be H, CH₃ or n--C₁₆ H₃₃ SO₂ --; R_(b) is hydrogen, C₁ -C₃₀ alkyl straight chain or branched [optionally mono- or disubstituted with HO-- or ##STR144## R_(c) is hydrogen, C₁ -C₃₀ alkyl straight chain or branched [optionally mono- or disubstituted with HO-- or ##STR145## R_(d) is hydrogen, C₁ -C₃₀ alkyl straight chain or branched [optionally substituted with HO--, Cl-- or ##STR146## and when R_(a) and R_(b) are taken together with the nitrogen they are attached to they represent a moiety of ##STR147## wherein R_(c) and R_(d) are defined as above;

organic cation X⁺ may also be imidazolium, pyridinium, quinolinium, dithiolium, tetrazolium or be represented by formula IIIb ##STR148## wherein R_(g) and R_(h) each are C₁ -C₃ alkyl; R_(j) is hydrogen, halogen, C₁ -C₃ alkyl or C₁ -C₃ alkoxy; R_(i) and R_(k) each are hydrogen C₁ -C₆ alkyl straight chain or branched, C₃ -C₆ cycloalkyl, ##STR149## wherein U and V each are hydrogen, halogen, C₁ -C₃ alkyl, C₁ -C₃ alkoxy, CN or CF₃ ; W is hydrogen or C₁ -C₃ alkyl; and each symol represents a single or double bond, wherein if both are single bonds then the cations are pyrazolidinium cations represented by formula IIIc ##STR150## wherein R_(g) to R_(k) are as defined above, and X⁺ may also be represented by formulae IIIf and IIIg

    R.sub.1 -P.sup.+ (Rm).sub.3                                IIIf

wherein R₁ is C₁ -C₆ alkyl, ##STR151## wherein U and V are as hereinabove defined; Rm is C₁ -C₆ alkyl or ##STR152## S⁺ R_(a) R_(b) R_(c) (IIIg) and I⁺ R_(a) R_(b) (IIIh), wherein R_(a), R_(b) and R_(c) are as hereinabove defined.

Another group of novel salts represented by formula (X) and of interest are graphically illustrated and described as follows: ##STR153## wherein R₂ and R₆ are Br, Cl, F, I, C₁ -C₄ alkyl, C₁ -C₄ haloalkyl, C₁ -C₄ haloalkoxy, SO₂ R₈, SR₈ or COR₁₀ ; R₃ is C₁ -C₄ alkyl, C₁ -C₄ alkoxy, NH₂, NHCOCH₃, Br, Cl, F, I, NO₂, SO₂ R₈, CN or CO₂ CH₃ ; R₄ is Br, Cl, F, I, C₁ -C₂ alkyl, SO₂ R₈, COR₉, CN, NHCOCH₃, SO₂ NR₁₀ R₁₁, ##STR154## phenoxy or substituted phenoxy and the substituents are CH₃, CF₃, CH₃ O, Br, Cl, F, I, NO₂ or OCH₂ CO₂ C₂ H₅ ; R₈ is C₁ -C₆ alkyl, phenyl or benzyl; R₉ is hydrogen, hydroxyl, C₁ -C₃ alkyl, C₁ -C₃ alkoxy or phenyl; R₁₀ and R₁₁ are hydrogen, C₁ -C₄ alkyl or phenyl; X⁺ is inorganic or organic,

when X is inorganic, it is alkali metals, alkaline earth metals, Co, Zn, or Ag;

when the cation X⁺ is organic, X⁺ is represented by formula IIIa

    N.sup.+ R.sub.a R.sub.b R.sub.c R.sub.d                    (IIIa)

wherein R_(a) is hydrogen, C₁ -C₃₀ alkyl straight chain or branched [optionally mono- or disubstituted with HO--, CH₃ O₂ C--, CH₃ S--, C₃ -C₁₈ alkenylaminoalkylene (C₁ -C₃), H₂ N, (CH₃)₂ N--, ##STR155## C₃ -C₆ alkenyl, C₃ -C₆ alkynyl, C₃ -C₆ cycloalkyl, ##STR156## wherein R_(e) and R_(f) each may be H, CH₃ or n-C₁₆ H₃₃ SO₂ --; R_(b) is hydrogen, C₁ -C₃₀ alkyl straight chain or branched [optionally mono- or disubstituted with HO-- or ##STR157## R_(c) is hydrogen, C₁ -C₃₀ alkyl straight chain or branched [optionally mono- or disubstituted with HO-- or ##STR158## R_(d) is hydrogen, C₁ -C₃₀ alkyl straight chain or branched [optionally substituted with HO--, Cl-- or ##STR159## and when R_(a) and R_(b) are taken together with the nitrogen they are attached to they represent a moiety of ##STR160## wherein R_(c) and R_(d) are defined as above;

organic cation X⁺ may also be imidazolium, pyridinium, quinolinium, dithiolium, tetrazolium or be represented by formula IIIb ##STR161## wherein R_(g) and R_(h) each are C₁ -C₃ alkyl; R_(j) is hydrogen, halogen, C₁ -C₃ alkyl or C₁ -C₃ alkoxy; R_(i) and R_(k) each are hydrogen C₁ -C₆ alkyl straight chain or branched, C₃ -C₆ cycloalkyl, ##STR162## wherein U and V each are hydrogen, halogen, C₁ -C₃ alkyl, C₁ -C₃ alkoxy, CN or CF₃ ; W is hydrogen or C₁ -C₃ alkyl; and each symbol represents a single or double bond, wherein if both are single bonds then the cations are pyrazolidinium cations represented by formula IIIc ##STR163## wherein R_(g) to R_(k) are as defined above; and

X⁺ may also be represented by formulae IIIf and IIIg

    R.sub.1 -P.sup.+ (Rm).sub.3                                IIIf

wherein R₁ is C₁ -C₆ alkyl, ##STR164## wherein U and V are as hereinabove defined; Rm is C₁ -C₆ alkyl or ##STR165## S⁺ R_(a) R_(b) R_(c) (IIIg) and I⁺ R_(a) R_(b) (IIIh), wherein R_(a), R_(b) and R_(c) are as hereinabove defined.

Still another group of novel salts represented by formula XI and of interest are graphically illustrated and described as follows: ##STR166## wherein R₁ is hydrogen, C₁ -C₃ alkyl, C₁ -C₃ haloalkyl, CN, Br, Cl, F, I, NO₂, SO₂ R₈, COR₉, phenyl or substituted phenyl and the substituents are CH₃, CF₃, CH₃ O, NO₂ or OCH₂ CO₂ C₂ H₅ ; R₂ and R₆ are hydrogen, Br, Cl, F, I, C₁ -C₄ alkyl, C₁ -C₄ haloalkyl, C₁ -C₄ haloalkoxy, SO₂ R₈, SR₈, COR₁₀ ; R₃ is hydrogen, C₁ -C₄ alkyl, C₁ -C₄ alkoxy, NH₂, NHCOCH₃, Br, Cl, F, I, NO₂, SO₂ R₈, CN or CO₂ CH₃ ; R₄ is hydrogen, Br, Cl, F, I, C₁ -C₂ alkyl, SO₂ R₈, COR₉, CN, NHCOCH₃, SO₂ NR₁₀ R₁₁, ##STR167## phenoxy or substituted phenoxy and the substituents are CH₃, CF₃, CH₃ O, Br, Cl, F, I, NO₂ or OCH₂ CO₂ C₂ H₅ ; R₈ is C₁ -C₆ alkyl, phenyl or benzyl; R₉ is hydrogen, hydroxyl, C₁ -C₃ alkyl, C₁ -C₃ alkoxy or phenyl; R₁₀ and R₁₁ are hydrogen, C₁ -C₄ alkyl or phenyl; X⁺ is inorganic or organic,

when X is inorganic, it is alkali metals, alkaline earth metals, Co, Zn, or Ag;

when the cation X⁺ is organic, X⁺ is represented by formula IIIa

    N.sup.+ R.sub.a R.sub.b R.sub.c R.sub.d                    (IIIa)

wherein R_(a) is hydrogen, C₁ -C₃₀ alkyl straight chain or branched [optionally mono- or disubstituted with HO--, CH₃ O₂ C--, CH₃ S--, C₃ -C₁₈ alkenylaminoalkylene (C₁ -C₃), H₂ N, (CH₃)₂ N--, ##STR168## C₃ -C₆ alkenyl, C₃ -C₆ alkynyl, C₃ -C₆ cycloalkyl, ##STR169## wherein R_(e) and R_(f) each may be H, CH₃ or n-C₁₆ H₃₃ SO₂ --; R_(b) is hydrogen, C₁ -C₃₀ alkyl straight chain or branched [optionally mono- or disubstituted with HO-- or ##STR170## R_(c) is hydrogen, C₁ -C₃₀ alkyl straight chain or branched [optionally mono- or disubstituted with HO-- or ##STR171## R_(d) is hydrogen, C₁ -C₃₀ alkyl straight chain or branched [optionally substituted with HO--, Cl-- or ##STR172## and when R_(a) and R_(b) are taken together with the nitrogen they are attached to they represent a moiety of ##STR173## wherein R_(c) and R_(d) are defined as above;

organic cation X⁺ may also be imidazolium, pyridinium, quinolinium, dithiolium, tetrazolium or be represented by formula IIIb ##STR174## wherein R_(g) and R_(h) each are C₁ -C₃ alkyl; R_(j) is hydrogen, halogen, C₁ -C₃ alkyl or C₁ -C₃ alkoxy; R_(i) and R_(k) each are hydrogen C₁ -C₆ alkyl straight chain or branched, C₃ -C₆ cycloalkyl, ##STR175## wherein U and V each are hydrogen, halogen, C₁ -C₃ alkyl, C₁ -C₃ alkoxy, CN or CF₃ ; W is hydrogen or C₁ -C₃ alkyl; and each symbol represents a single or double bond, wherein if both are single bonds then the cations are pyrazolidinium cations represented by formula IIIc ##STR176## wherein R_(g) to R_(k) are as defined above, and

X⁺ may also be represented by formulae IIIf and IIIg

    R.sub.1 -P.sup.+ (Rm).sub.3                                IIIf

wherein R₁ is C₁ -C₆ alkyl, ##STR177## wherein U and V are as hereinabove defined; Rm is C₁ -C₆ alkyl or ##STR178## S⁺ R_(a) R_(b) R_(c) (IIIa) and I⁺ R_(a) R_(b) (IIIh), wherein R_(a), R_(b) and R_(c) are as hereinabove defined.

The invention relates to methods for treating graminaceous crops, leguminous crops, cotton, sunflowers and herbaceous ornamental plants to increase axillary branching, improve the canopy and enhance flowering thereof. Surprisingly, application of the above-said salts to the foliage of the above-identified crops has the further advantage that said salts produce a dwarfing effect in said plants while increasing the stem stiffness thereof. They also enhance yield therefrom.

Dwarfing and/or stiffening of the stems of cotton, legumes, graminaceous crops and sunflowers is most advantageous to the farmer since lodging of these crops usually results in reduced yields of the affected crops.

Lodging, in the present application, refers to the deflection of the plant from the vertical, varying in degree from only a slight deflection to complete deflection (i.e. plants prone) caused by, in most cases, the action of wind and/or rain on the plants. This deflection is such that when the causal agent (wind, rain) is no longer present the deflection is neither immediately nor completely overcome. Moreover, where extensive or severe lodging has occurred, the crop may be difficult to harvest and the yield markedly reduced.

In practice we have found that application to the foliage of seedling plants of from about 0.06 to 2.0 kg/ha and preferably about 0.125 to 0.50 kg/ha is sufficient to achieve the several desirable and advantageous biological responses in plants described above.

Inasmuch as the salts or compounds of formula (I) of the present invention have only limited solubility in water, they are generally formulated for foliar application as wettable powders, flowable dispersions or emulsion concentrates, which are usually dispersed in water on in other, inexpensive, liquid diluents for application to the foliage of said plants as a liquid spray.

A typical wettable powder can be prepared by grinding together approximately 46% by weight of a finely divided carrier such as attapulgite, 50% by weight of the pyrazolium, pyrazolinium or pyrazolidine salt of 2,4,6-trisubstituted-N-nitroaniline, 3% by weight of the sodium salt of condensed naphthalene sulfonic acids and 1% by weight of sodium N-methyl-N-oleoyltaurate.

A typical flowable dispersion can be prepared by admixing about 42% by weight of the N-nitroaniline salt with about 3% by weight of the sodium salt of condensed naphthalene sulfonic acids, 2% by weight of finely divided bentonite and 53% by weight of water.

Emulsion concentrated may be prepared by dissolving 15% to 70% by weight of the formula (I) compound in 85% to 30% of a solvent such as N-methylpyrrolidone, lower alcohols, methylisobutylketone, 2-methoxy ethanol, propylene glycol, diethylene glycol, diethylene glycol monomethyl ether, formamide, methylformamide, and the like, and mixtures thereof. Advantageously, surfactants such as polyoxyethylated vegetable oil or an alkyl phenoxy polyoxyethylene ethanol are also incorporated in amounts of 1% to 5% by weight of said concentrate.

In accordance with this invention, the trisubstituted-N-nitroanilines (phenylnitramines) can be prepared from the corresponding substituted anilines by a variety of conventional procedures. For illustrative purposes, one such procedure is hereinbelow graphically illustrated and described as follows: ##STR179## wherein R₂, R₄ and R₆ are as defined above. The above synthesis is conveniently carried out in a solvent, such as acetic acid, preferably in the presence of acetic anhydride. The product may be precipitated from the reaction mixture by the addition of ice water. Purification may be effected by conventional procedures such as recrystallization, chromatography, and the like.

The nitroanilines, wherein R₂ and/or R₆ are haloalkyl or hydroxyalkyl and R₄ is halogen, can be prepared by a two-step synthesis involving Step 1, the reaction of the appropriate haloalkyl aniline or haloalkoxyaniline with halogen (e.g. chlorine or bromine) in the presence of an acid acceptor such as sodium acetate, potassium acetate, or the like, in the presence of an inert organic solvent (e.g. tert-butanol, CCl₄, ethylene dichloride, chlorobenzene, or the like). The reaction is generally conducted at a temperature in the range of from 25° C. to 75° C., and preferably at a temperature of about 45° to 55° C. The reaction yields the corresponding 2,4,6-trisubstituted aniline, which may then be converted, in Step 2, to the corresponding 2,4,6-trisubstituted N-nitroaniline by reaction with nitric acid in the presence of a solvent, such as acetic acid, and acetic anhydride. Steps 1 and 2 can be graphically illustrated as follows: ##STR180## wherein R₂ and R₆ are haloalkyl or haloalkoxy, and R₄ is chlorine or bromine. ##STR181##

The formula (II) salts of the substituted -N-nitroaniline compounds can be conveniently prepared from the substituted nitroaniline compounds by one or more procedures, hereinafter referred to as Methods A,B,C,D or E.

Methods for the preparation of salts of 2,4,6-trisubstituted N-nitroanilines Method A

The N-nitroaniline is dissolved in dilute aqueous sodium or potassium hydroxide and filtered. To this solution is added one molar equivalent of the appropriate salt and dissolved in water. In most cases the product separates as a solid, and is removed by filtration and purified by recrystallization. Whenever no precipitation occurs or the product separates as an oil, an extraction with methylene chloride is performed. Concentration of this extract yields the product which may be further purified by recrystallization.

Method B

A solution of the N-nitroaniline in anhydrous ether is treated with a solution of one equivalent of the appropriate nitrogen base in ether. The desired product is removed by filtration and purified by washing and recrystallization. Precipitation of the product may be promoted by the addition of petroleum ether.

Method C

To a methanolic suspension of the silver salt of the N-nitroaniline is added one equivalent of the halide salt of the appropriate amine dissolved in methanol. The mixture is stirred at 25° C. for one hour. The precipitated silver halide is removed by filtration, the product is recovered by evaporating the methanolic solution and purified by recrystallization.

Method D

An aqueous solution of the sodium salt of the N-nitroaniline is saturated with a large excess of the desired metal salt until solids remain undissolved. After stirring for one hour, the solids are removed by filtration and recrystallized or washed with a suitable solvent, and dried.

Method E

A methylene chloride solution of the free N-nitroaniline is treated with a three-fold excess of an aqueous solution of the appropriate metal hydroxide, acetate or carbonate. If precipitation occurs, the product is removed by filtration and recrystallized. Otherwise, the aqueous layer is separated and evaporated to dryness. The residue is treated with ethyl acetate and filtered. Removal of the ethyl acetate affords the product which may be recrystallized, if necessary.

Formula (I) compounds wherein R₇ is a substituent other than hydrogen may be conveniently prepared as follows:

The appropriately substituted formula (I) compound (R₇ =hydrogen) is reacted in with an alcoholic solution of 1 equivalent of sodium hydroxide in the presence of a lower alcohol such as methanol, and the thus formed sodium salt is isolated by evaporating the reaction mixture to dryness. Next, the sodium salt is dissolved in dimethyl sulfoxide (DMSO) and treated with the appropriate alkyl halide at a temperature range from about 20° C. to about 30° C., preferably 25° C. for a period of time sufficient to essentially complete the reaction. The reaction mixture is then poured into water, the product extracted with a water immiscible solvent such as ether and recovered from said extract by standard laboratory procedures. The above reaction sequence may be graphically illustrated as follows: ##STR182## Wherein in the above reaction sequence Q is halogen, n, R, to R₇ are as hereinabove defined except that in the R₇ -Q formula R₇ cannot be hydrogen.

Formula (Ia) phenylnitramines may be prepared by the following route:

A formula II silver salt is suspended in ether under an inert atmosphere such as N₂, and reacted with 1:1 equivalent of the appropriate R₇ -Q compound at a temperature range of from about 20° C. to about 30° C. and preferably 25° C. for a period of time sufficient to essentially complete the reaction. The thus obtained O-alkyl derivative of formula (Ia) structure is isolated and purified by standard laboratory procedures. The above reaction sequence may be graphically illustrated as follows: ##STR183##

It is recognized of course, that in the course of the preparation of formula (I) compounds wherein R₇ is other than hydrogen formula (Ia) compounds are also formed, and vice versa.

Formula (I) compounds wherein n is 1 and R₇ is hydrogen may be conveniently prepared as follows:

A solution of the appropriate benzyl halide or mesylate and ammonium nitrourethane is heated in the presence of dry dimethyl sulfoxide at about 80° C. for about 4 hours or a period of time sufficient to essentially complete the reaction. The reaction mixture is then cooled down, poured in water extracted with a water immiscible organic solvent such as ether and the solution dried over anhydrous magnesium sulfate. Next, anhydrous ammonia gas is bubbled through the solution. The precipitated material is then isolated, dissolved in water and precipitated from the aqueous solution with a dilute acid. The thus obtained product is then isolated by standard laboratory methods and further purified, if so desired. The above reaction sequence may be graphically illustrated as follows: ##STR184## Wherein R₁ to R₆ are as hereinabove defined, Y is Br, Cl or CH₃ SO₃.

The intermediate substituted anilines may also be N-nitrated to yield the corresponding N-nitroanilines as follows:

Diisopropylamine is lithiated with an equimolar amount of n-butyllithium in an inert solvent such as ether at about -75° to -80° C. Next a solution of the appropriately substituted aniline is added to the above mixture at about -60° C., the reaction mixture warmed to about 0° C. and methyl nitrate added. The reaction mixture is allowed to warm slowly to room temperature and the product product isolated by standard laboratory procedures.

Surprisingly, it has also been found that the formula I compounds of this invention are effective for reducing the relative stem growth of broadleaf plants and for increasing the stem stiffness thereof, particularly for broadleaf agronomic crops such as sunflowers, when said compounds are applied preemergence to soil in which seeds of said plants have been sown. When used in this manner said formula I compounds are generally applied at rates of from 0.125 to 2.0 and preferably 0.25 to 0.75 kg/ha.

The invention is further illustrated by the Examples set forth below which are not intended to be limiting on the invention.

EXAMPLE 1 Methods for the preparation of salts of 2,4,6-trisubstituted N-nitroanilines Method A

The N-nitroaniline is dissolved in dilute aqueous sodium or potassium hydroxide and filtered. To this solution is added one molar equivalent of the appropriate salt and dissolved in water. In most cases the product separates as a solid, and is removed by filtration and purified by recrystallization. Whenever no precipitation occurs or the product separates as an oil, an extraction with methylene chloride is performed. Concentration of this extract yields the product which may be further purified by recrystallization.

Method B

A solution of the N-nitroaniline in anhydrous ether is treated with a solution of one equivalent of the appropriate nitrogen base in ether. The desired product is removed by filtration and purified by washing and recrystallization. Precipitation of the product may be promoted by the addition of petroleum ether.

Method C

To a methanolic suspension of the silver salt of the N-nitroaniline is added one equivalent of the halide salt of the appropriate amine dissolved in methanol. The mixture is stirred at 25° C. for one hour. The precipitated silver halide is removed by filtration, the product recovered by evaporating the methanolic solution and purified by recrystallization.

Method D

An aqueous solution of the sodium salt of the N-nitroaniline is saturated with a large excess of the desired metal salt until solids remain undissolved. After stirring for one hour, the solids are removed by filtration and recrystallized or washed with a suitable solvent, and dried.

Method E

A methylene chloride solution of the free N-nitroaniline is treated with a three-fold excess of an aqueous solution of the appropriate metal hydroxide, acetate or carbonate. If precipitation occurs, the product is removed by filtration and recrystallized. Otherwise, the aqueous layer is separated and evaporated to dryness. The residue is treated with ethyl acetate and filtered. Removal of the ethyl acetate affords the product which may be recrystallized, if necessary.

By the above methods a number of compounds are prepared, these are listed in Tables appended hereto.

                  TABLE I                                                          ______________________________________                                         Inorganic salts of 2,4,6-tribromo-N--aci-nitroaniline                          and other 2,4,6-trisubstituted N--aci-nitroanilines                            ______________________________________                                                Analysis       M.P.                                                     No   X.sup.+ Calculated                                                                               Found    (°C.)                                                                          Method                                  ______________________________________                                         1    Na.sup.+                                                                               C      16.64                                                                               C    16.74 260    E                                                H       1.40                                                                               H     1.31 (dec)                                                   N       6.47                                                                               N     6.40                                            2    K.sup.+ C      16.72                                                                               C    17.19 >230   E                                                H       0.94                                                                               H     0.74                                                         N       6.50                                                                               N     6.26                                            3    Li.sup.+                                                                               H       1.61                                                                               H     1.46 284-   E                                                N       7.03                                                                               N     6.90 288                                                     Br     60.12                                                                               Br   60.43 (dec)                                                   Li      1.74                                                                               Li    1.59                                            4    Ca.sup.2+                                                                              C      16.78                                                                               C    16.29 240    D                                                H       1.40                                                                               H     1.08 (dec)                                                   N       6.52                                                                               N     6.34                                                         Br     55.82                                                                               Br   56.03                                            5    Mg.sup.2+                                                                              C      16.37                                                                               C    16.62 129-   E                                                H       1.83                                                                               H     2.45 135                                                     N       6.37                                                                               N     5.71 (dec)                                                   Mg      2.76                                                                               Mg    3.27                                            6    Ba.sup.2+                                                                              C      15.65                                                                               C    15.37 202-   D                                                H       0.88                                                                               H     0.86 208                                                     N       6.08                                                                               N     6.07                                                         Ba     14.91                                                                               Ba   14.96                                            7    Sr.sup.2+                      216-   D                                                                       219                                                                            (dec)                                      ______________________________________                                                Analysis       M.P.                                                     No   M.sup.+ Calculated                                                                               Found    (°C.)                                                                          Method                                  ______________________________________                                         8    Co.sup.2+                                                                              N       6.65                                                                               N     6.36 172-   C                                                Co      6.99                                                                               Co    6.79 176                                                                            (dec)                                      9    Zn.sup.2+                                                                              C      17.73                                                                               C    18.16 110-   D                                                                       130                                                                            (dec)                                      10   Ag.sup.+                       176-   D                                                                       190                                                                            (dec)                                      ______________________________________                                    

                                      TABLE Ia                                     __________________________________________________________________________     Inorganic salts of 2,4,6 trisubstituted formual (II) compounds of              structure                                                                       ##STR185##                                                                                    Analysis   M.P.                                                No                                                                               R.sup.2                                                                             R.sup.4                                                                           R.sup.6                                                                           X+ Calculated                                                                           Found                                                                               (°C.)                                                                        Method                                         __________________________________________________________________________     1 CO.sub.2 C.sub.2 H.sub.5                                                            Br Br K.sup.+                                                                           C  25.72                                                                             C  25.32                                                                            232-234                                                                             E                                                              H  2.13                                                                              H  2.02                                                                             (dec)                                                               N  6.60                                                                              N  6.40                                                  2 Br   Br I  Na.sup.+                                                          3 Cl   I  Cl Na.sup.+                                                          4 CF.sub.3                                                                            Br Br Na.sup.+                                                                          C  20.81                                                                             C  21.05                                                                            223-226                                                                             E                                                              H  1.00    (dec)                                                               N  6.94                                                                              N  67.48                                                                 Br39.56                                                                              Br39.47                                                                  F 14.40                                                                              F 14.13                                                                  Na 5.70                                                                              Na 5.87                                                  5 CH.sub.3                                                                            CH.sub.3                                                                          CH.sub.3                                                                          Na.sup.+                                                          6 Cl   Cl Cl Na.sup.+                                                          7 Cl   Cl Br Na.sup.+                                                          8 Br   CN Br Na.sup.+      >250 E                                              9 Br   CH.sub.3                                                                          Br Na.sup.+      >230 E                                              __________________________________________________________________________

                  TABLE Ib                                                         ______________________________________                                         Sodium salts of formula II compounds of structure                               ##STR186##                                                                    No.   R.sub.2  R.sub.3                                                                               R.sub.4                                                                               R.sub.5                                                                             R.sub.6                                                                             mp °C.                           ______________________________________                                         1     Br       Br            Br   Br   200 (dec)                               2     Br                          C.sub.2 H.sub.5                                                                     >250                                    3     CH.sub.3        Br          CH.sub.3                                                                            190-200 (dec)                           4     Br              CH.sub.3    Br   >260                                    5     CH.sub.3                    CH.sub.3                                                                            gum                                     6     C.sub.2 H.sub.5             C.sub.2 H.sub.5                                                                     gum                                     7     Br                               74-75                                   8     Br                          Br   >200                                    9     Cl       Cl                      260 (dec)                               10    Br              Br          C.sub.2 H.sub.5                                                                     250 (dec)                               11    Br              C.sub.2 H.sub.5                                                                            Br   252 (dec)                               12    Cl              I           Cl   >250                                    13                    CH.sub.3 SO.sub.2                                                                               >300                                    14                    COC.sub.6 H.sub.5                                                                               254-255                                 15    COC.sub.6 H.sub.5                89-91                                   ______________________________________                                    

                                      TABLE Ic                                     __________________________________________________________________________     Primary amine salts of 2,4,6-tribromo-Naci-nitroaniline                                                   Analysis   M.P.                                     No X.sup.+                 Calculated                                                                           Found                                                                               (°C.)                                                                          Method                            __________________________________________________________________________     1  NH.sub.4.sup.+          C  18.39                                                                             C  18.43                                                                            164    B                                                            H  1.54                                                                              H  1.54                                                                  N  10.72                                                                             N  10.72                                      2  CH.sub.3 NH.sub.3.sup.+ C  20.71                                                                             C  20.80                                                                            157-164                                                                               B                                                            H  1.99                                                                              H  1.97                                                                  N  10.35                                                                             N  10.35                                                                 Br59.07                                                                              Br59.07                                       3  C.sub.2 H.sub.5 NH.sub.3.sup.+     140-141 (dec)                                                                         B                                 4  n-C.sub.3 H.sub.7 NH.sub.3.sup.+   153 (dec)                                                                             B                                 5  i-C.sub.3 H.sub.7 NH.sub.3.sup.+                                            6  n-C.sub.4 H.sub.9 NH.sub.3.sup.+                                            7  sec-C.sub.4 H.sub.9 NH.sub.3.sup.+ 137-138 (dec)                                                                         B                                 8  i-C.sub.4 H.sub.9 NH.sub.3.sup.+                                            9  t-C.sub.4 H.sub.9 NH.sub.3         178-180                                                                        (slow dec)                               10 n-C.sub.5 H.sub.11 NH.sub.3.sup.+  131-132                                                                               B                                 11 n-C.sub.6 H.sub.13 NH.sub.3.sup.+                                           12 n-C.sub.8 H.sub.17 NH.sub.3.sup.+                                                                      C  33.36                                                                             C  33.58                                                                            78-81  B                                                            H  4.40                                                                              H  4.58                                                                  N  8.34                                                                              N  8.34                                                                  Br47.56                                                                              Br47.52                                       13 n-C.sub.12 H.sub.25 NH.sub.3.sup.+                                                                     C  38.59                                                                             C  38.80                                                                            91-92  B                                                            H  5.40                                                                              H  5.40                                                                  N  7.50                                                                              N  7.35                                                                  Br42.30                                                                              Br42.20                                       14 n-C.sub.14 H.sub.29 NH.sub.3.sup.+                                          15 n-C.sub.16 H.sub.33 NH.sub.3.sup.+                                          16 n-C.sub.18 H.sub.35 NH.sub.3.sup.+                                                                     C  44.73                                                                             C  45.08                                                                            75-77  B                                                            H  6.57                                                                              H  6.65                                                                  N  6.52                                                                              N  6.71                                                                  Br37.21                                                                              Br37.57                                       17 n-C.sub.18 H.sub.37 NH.sub.3.sup.+ 76-77  B                                 18 n-C.sub.20 H.sub.42 NH.sub.3.sup.+ 79-80  B                                 19 n-C.sub.22 H.sub.45 NH.sub.3.sup.+ 74-76  B                                 20 n-C.sub.30 H.sub.62 NH.sub.3.sup.+                                          21 H.sub.2 CCHCH.sub.2 NH.sub.3.sup.+ 145-146                                                                               A                                 22 HCCCH.sub.2NH.sub.3.sup.+          136-138 (dec)                                                                         B                                 23 HOCH.sub.2 CH.sub.2 NH.sub.3.sup.+                                                                     C  22.04                                                                             C  22.08                                                                            168-169                                                                               B                                                            H  2.31                                                                              H  2.38                                                                  N  9.57                                                                              N  9.64                                                                  Br55.00                                                                              Br55.05                                       24                                                                                 ##STR187##             C  30.02 H  3.49 N  8.08 Br46.10                                                     C  30.26 H  3.52 N  7.99 Br46.21                                                    129-131                                                                               B                                 25 CH.sub.3 S(CH.sub.2).sub.3 NH.sub.3.sup.+                                                                         102-103 (dec)                            26 C.sub.8 H.sub.17 CHCHC.sub.8 H.sub.16NHC.sub.3 H.sub.6 NH.sub.3.sup.+                                  N  6.77                                                                              N  6.73                                                                             90-96  B                                 27 C.sub.8 H.sub.17 CHCHCH.sub.2CHCHC.sub. 5 H.sub.10 NH.sub.3.sup.+                                      H  5.98                                                                              H  6.44                                                                             Wax    B                                                            N  6.56                                                                              N  6.37                                       28 C.sub.8 H.sub.17 CHCHC.sub.8 H.sub.16 NH.sub.3.sup.+                                                              74     A                                 29                                                                                 ##STR188##                        170-175 (dec)                                                                         B                                 30                                                                                 ##STR189##                                                                 31                                                                                 ##STR190##             C  30.80 H  2.15 N  8.98                                                             C  30.72 H  2.07 N  8.83                                                            78-85  B                                 32                                                                                 ##STR191##                        86-87  B                                 33                                                                                 ##STR192##                                                                 34                                                                                 ##STR193##                                                                 35                                                                                 ##STR194##                                                                 36                                                                                 ##STR195##                                                                 37 4-(n-C.sub.16 H.sub.33 SO.sub.2)C.sub.6 H.sub.4.sup.+NH.sub.3               38                                                                                 ##STR196##                        154-155                                                                               B                                 39 (CH.sub.3).sub.2 N.sup.+NH.sub.3                                            __________________________________________________________________________

                  TABLE Id                                                         ______________________________________                                         Tallowamine salts of miscellaneous Naci-nitroanilines of                        ##STR197##                                                                                     Analysis                                                                                        Calcu-       M.P.                            No  R.sub.2                                                                               R.sub.3                                                                              R.sub.4                                                                            R.sub.5                                                                            R.sub.6  lated  Found °C.                      ______________________________________                                          1  Br                   C.sub.2 H.sub.5                                                                        C  60.93                                                                              C  60.72                                                                              gum                                                              H  9.05                                                                               H  9.60                                                                 N  8.20                                                                               N  8.35                                 2  CH.sub.3     Br      CH.sub.3                                                                               C  60.90                                                                              C  60.90                                                                              gum                                                              H  9.04                                                                               H  9.25                                                                 N  8.25                                                                               N  8.29                                                                 Br15.58                                                                               Br15.52                                 3  C.sub.2 H.sub.5                                                                                      ##STR198##                                                                            C  73.57 H  11.32 N  8.58                                                             C 73.01 H 11.83 N                                                                     gum7                             4  Br     Br        Br  Br                    110-                                                                           112                              5  CH.sub.3             CH.sub.3                                                                               C 71.67                                                                               C 71.58                                                                               gum                                                              H  11.34                                                                              H  11.61                                                                N  9.65                                                                               N  9.64                                 6  C.sub.2 H.sub.5      C.sub.2 H.sub.5                                                                        C  72.52                                                                              C  72.20                                                                              gum                                                              H  11.52                                                                              H  11.61                                                                N  9.06                                                                               N  9.02                                 7  Br                   Br      H  7.68                                                                               H  7.29                                                                               wax                                                              N  7.43                                                                               N  7.43                                 8  C.sub.2 H.sub.5      CH(CH.sub.3).sub.2                                                                     C  73.21                                                                              C  73.22                                                                              gum                                                              N  8.83                                                                               N  8.48                                 9  CH.sub.3             CH(CH.sub.3).sub.2                                                                     C  73.21                                                                              C  73.22                                                                              gum                                                              N  8.83                                                                               N  8.48                                10  CH.sub.3             C(CH.sub.3).sub.3                                                                      H  11.23                                                                              H  11.53                                                                              gum                                                              N  8.33                                                                               N  9.07                                11  Cl           I       Cl                    70-72                           12  Br               Br                        25-30                           ______________________________________                                    

                  TABLE Ie                                                         ______________________________________                                         Secondary amine salts of 2,4,6-tribromo-Naci-nitroaniline                                  Analysis                                                                              Calcu-         M.P.                                         No  X.sup.+        lated    Found (°C.)                                                                         Method                                 ______________________________________                                          1  (CH.sub.3).sub.2 NH.sub.2.sup.+                                                                              164.5-                                                                         165.5                                                                          (dec)                                         2  (C.sub.2 H.sub.5).sub.2 NH.sub.2.sup.+                                                                       156-  B                                                                        160                                           3  (n-C.sub.3 H.sub.7).sub.2 NH.sub.2.sup.+                                    4  [(CH.sub.3).sub.2 CH].sub.2 NH.sub.2.sup.+                                                   C  30.28 C  30.63                                                                              164-  B                                                        H  3.81  H  3.94                                                                               171                                                            N  8.83  N  8.75                                              5  (n-C.sub.4 H.sub.9).sub.2 NH.sub.2.sup.+                                                                     166-  B                                                                        169                                                                            (dec)                                         6  (C.sub.18 H.sub.37).sub.2 NH.sub.2.sup.+                                    7  (HOCH.sub.2 CH.sub.2).sub.2.sup.+NH.sub.2                                                                    158-  B                                                                        159                                                                            (dec)                                         8  (C.sub.6 H.sub.5CH.sub.2).sub.2 N.sup.+H.sub.2                                               C  41.98 C  41.27                                                                              168-  B                                                        H  3.17  H  3.24                                                                               169                                                            N  7.34  N  7.28                                                                               (dec)                                                          Br41.91  Br42.16                                              9                                                                                  ##STR199##                                                                10                                                                                  ##STR200##                   155- 158                                                                             B                                      11                                                                                  ##STR201##                   161- 163 (dec)                                                                       B                                      12                                                                                  ##STR202##   C  26.60 H  2.62 N  9.10                                                                C  26.10 H  2.62 N  9.04                                                              157- 158 (dec)                               13                                                                                  ##STR203##                   156- 158 (dec)                                                                       B                                      ______________________________________                                    

                                      TABLE If                                     __________________________________________________________________________     Secondary amine salts of various di-and trisubstituted Naci-nitroanilines       ##STR204##                                                                                              Analysis   M.P.                                      No R.sub.2                                                                          R.sub.4                                                                            R.sub.6                                                                              X.sup.+    Calculated                                                                           Found                                                                               (°C.)                                                                        Method                               __________________________________________________________________________     1  Br                                                                               F   F     [(CH.sub.3).sub.2 CH].sub.2 .sup.+NH.sub.2                                                C  40.92                                                                             C  40.66                                                                            156-162                                                                             B                                                              H  4.58                                                                              H  5.12                                                                  N  11.93                                                                             N  11.84                                                                 Br27.69                                                                              Br27.43                                                                  F 10.79                                                                              F 10.66                                        2  Br                                                                               Br  i-Pr  [(CH.sub.3).sub.2 CH].sub.2.sup.+NH.sub.2                                                 C  41.11                                                                             C  40.98                                                                            144-157                                                                             B                                                              H  5.52                                                                              H  5.56                                                                  N  9.59                                                                              N  9.56                                        3  F F   F     [(CH.sub.3).sub.2 CH].sub.2.sup.+NH.sub.2                                                 C  49.14                                                                             C  49.35                                                                            148-161                                                                             B                                                              H  6.19                                                                              H  6.26                                                                  N  14.33                                                                             N  14.27                                                                 F 19.14                                                                              F 19.29                                        4  Br                                                                               i-Pr                                                                               Br    [(CH.sub.3).sub.2 CH].sub.2.sup.+NH.sub.2                                                 C  41.02                                                                             C  41.06                                                                            168-175                                                                             B                                                              H  5.74                                                                              H  5.42                                                                  N  9.57                                                                              N  9.62                                                                  Br36.39                                                                              Br36.66                                        5  Br                                                                               Br  OCH.sub.3                                                                            [(CH.sub.3).sub.2 CH].sub.2.sup.+NH.sub.2                                                 C  36.55                                                                             C  37.11                                                                            139-145                                                                             B                                                              H  4.96                                                                              H  5.51                                                                  N  9.84                                                                              N  10.15                                       6  Br                                                                               Br  SO.sub.2 CHF.sub.2                                                                   [(CH.sub.3).sub.2 CH].sub.2.sup.+ NH.sub.2                                                N  3.75                                                                              N  3.54                                                                             162-164                                                                             B                                                              F 7.43                                                                               F 7.38                                         7  Br                                                                               OCH.sub.3                                                                          Br    [(CH.sub.3).sub.2 CH].sub.2.sup.+NH.sub.2                                                 C  36.55                                                                             C  37.06                                                                            148-150                                                                             B                                                              H  4.96                                                                              H  5.03                                                                  N  9.84                                                                              N  9.68                                                                  Br37.42                                                                              Br36.24                                        8  I I   Cl    [(CH.sub.3).sub.2 CH].sub.2.sup.+NH.sub.2                                                 C  27.42                                                                             C  27.53                                                                            182-183                                                                             B                                                              H  3.45                                                                              H  3.52                                                                  N  8.0                                                                               N  7.91                                                                  Cl 7.43                                                                              Cl 7.38                                        9  Br                                                                               Br  SO.sub.2 F                                                                           [(CH.sub.3).sub.2 CH].sub.2.sup.+NH.sub.2                                                            118  B                                    10 Br                                                                               H   Br    (HOCH.sub.2 CH.sub.2).sub.2 NH.sub.2.sup.+                                                           115-118                                   __________________________________________________________________________

                  TABLE Ig                                                         ______________________________________                                         Tertiary amine salts with 2,4,6-tribromo-Naci-nitroaniline                                 Analysis                                                                             Calcu-        M.P.                                           No  X.sup.+       lated   Found (°C.)                                                                          Method                                  ______________________________________                                         1   (CH.sub.3).sub.3.sup.+NH    138-140                                                                        dec >160                                       2   (C.sub.2 H.sub.5).sub.3.sup.+NH                                                              C 30.28 C 30.33                                                                              128-135                                                                               B                                                         H 3.81  H 3.82                                                                               (dec)                                                            N 8.83  N 8.81                                               3   (n-C.sub.3 H.sub.7).sub.3.sup.+NH  B                                       4   (HOC.sub.2 H.sub.4).sub.3.sup.+NH                                                            C 27.50 C 28.39                                                                               79-81 B                                                         H 3.46  H 3.85                                                                 N 8.02  N 7.86                                                    ##STR205##                 107-110                                                                               B                                       6                                                                                   ##STR206##                 150-155                                                                               B                                       7                                                                                   ##STR207##                 127-134                                                                               B                                       8                                                                                   ##STR208##                 105-5 108                                                                             B                                       ______________________________________                                    

                                      TABLE Ih                                     __________________________________________________________________________     Quaternary amine salts of 2,4,6-tribromo-Naci-nitroaniline                                                     Analysis   M.P.                                No X.sup.+                      Calculated                                                                           Found                                                                               (°C.)                                                                          Method                       __________________________________________________________________________     1  (CH.sub.3).sub.4 N.sup.+     C  26.28                                                                             C  26.47                                                                            212-214                                                                               A                                                            H  3.31                                                                              H  3.19                                                                             (dec)                                                               N  9.19                                                                              N  9.40                                  2  (C.sub.2 H.sub.5).sub.4 N.sup.+                                                                             C  33.35                                                                             C  33.51                                                                            126-129                                                                               A                                                            H  4.40                                                                              H  4.31                                                                             (dec)                                                               N  8.34                                                                              N  8.50                                  3  (n-C.sub.3 H.sub.7).sub.4 N.sup.+                                           4  (n-C.sub.4 H.sub.9).sub.4 N.sup. +                                                                          C  42.87                                                                             C  42.83                                                                            102-106                                                             H  6.21                                                                              H  6.38                                                                  N  6.82                                                                              N  6.67                                  5  (n-C.sub.10 H.sub.23).sub.3.sup.+NCH.sub.3                                                                             oil    A                            6  n-C.sub.16 H.sub.33.sup.+N(CH.sub.3).sub.3                                  7  ClCH.sub.2 CH.sub.2.sup.+N(CH.sub.3).sub.3                                                                  C  26.60                                                                             C  27.05                                                                            124-125                                                                               C                                                            H  3.05                                                                              H  3.05                                                                  N  8.46                                                                              N  8.34                                                                  Br48.30                                                                              Br47.70                                  8  HOCH.sub.2 CH.sub.2.sup.+N(CH.sub.3).sub.3                                                                             177    C                                                                       (dec)                                   ##STR209##                  C  31.99 H  3.72 N  8.61 Br49.10                                                     C  32.06 H  3.75 N                                                                  160-16150.58                                                                          C                            10                                                                                 ##STR210##                             193-194 (dec)                                                                         C                            11                                                                                 ##STR211##                  C  40.31 H  4.27 N  7.42 Br42.35                                                     C  40.44 H  4.27 N                                                                  102-10442.67                                                                          A                            12                                                                                 ##STR212##                  C  47.80 H  5.94 N  6.19                                                             C  47.52 H  5.47 N                                                                   99-100                                                                               A                            13                                                                                 ##STR213##                             196-198                                                                               A                            14                                                                                 ##STR214##                             150-151                             15                                                                                 ##STR215##                             183-184 (dec)                                                                         C                            16                                                                                 ##STR216##                  H  5.64 N  5.34 Br 30.48                                                             H  5.62 N   5.39 Br 31.06                                                           110-112                                                                               A                            __________________________________________________________________________

                  TABLE Ii                                                         ______________________________________                                         Miscellaneous salts of 2,4,6-tribromo-N--aci-nitroaniline                                                           Meth-                                     No   X.sup.+              M.P. °C.                                                                           od                                        ______________________________________                                         1    (C.sub.6 H.sub.5).sub.3 S.sup.+                                                                     142-149 (dec)                                                                             C                                               ##STR217##          165-166 (dec)                                                                             A                                         3                                                                                    ##STR218##          150-151    A                                         4                                                                                    ##STR219##          154-159    A                                         5                                                                                    ##STR220##          118-121    A                                         6                                                                                    ##STR221##          180-184    C                                         7                                                                                    ##STR222##          40-45      B                                         8                                                                                    ##STR223##                     A                                         9                                                                                    ##STR224##          82         A                                         10                                                                                   ##STR225##          141-151 (dec)                                                                             C                                         11                                                                                   ##STR226##          48-53 (hygroscopic)                                                                       B                                         12                                                                                   ##STR227##          189-192 (dec)                                                                             B                                         13                                                                                   ##STR228##          160 (dec)  B                                         14                                                                                   ##STR229##          194-195 (dec)                                                                             A                                         15                                                                                   ##STR230##          77-80      B                                         16                                                                                   ##STR231##          113        C                                         17                                                                                   ##STR232##          110-112    B                                         18                                                                                   ##STR233##          131-132    B                                         19                                                                                   ##STR234##          160-162 (dec)                                                                             B                                         20                                                                                   ##STR235##          138-140 (dec)                                                                             B                                         21                                                                                   ##STR236##          80 (dec)   B                                         22                                                                                   ##STR237##          80-84      B                                         23                                                                                   ##STR238##          145        A                                         24                                                                                   ##STR239##          150-152    A                                         25                                                                                   ##STR240##          124-126    A                                         26                                                                                   ##STR241##                                                               27                                                                                   ##STR242##                                                               28                                                                                   ##STR243##                                                               29                                                                                   ##STR244##                                                               ______________________________________                                    

                                      TABLE Ij                                     __________________________________________________________________________     Salts of Formula:                                                               ##STR245##                                                                                               Analysis   M.P.                                     No R.sub.g                                                                           R.sub.h                                                                           R.sub.i  R.sub.j                                                                            R.sub.k                                                                             Calculated                                                                           Found                                                                               (°C.)                             __________________________________________________________________________     1  CH.sub.3                                                                          CH.sub.3                                                                          C.sub.6 H.sub.5                                                                         H   C.sub.6 H.sub.5                                                                     C  44.33                                                                             C 44.65                                                                             145-                                                                H   3.07                                                                             H  3.21                                                                             146                                                                 N   8.99                                                                             N  8.80                                                                             (dec)                                                               Br 38.47                                                                             Br                                                                               38.44                                       2  CH.sub.3                                                                          CH.sub.3                                                                          C.sub.6 H.sub.5                                                                         OCH.sub.3                                                                          C.sub.6 H.sub.5                                                                     C  44.13                                                                             C 44.11                                                                             41-44                                                               H   3.24                                                                             H  3.45                                                                  N   8.58                                                                             N  8.42                                       3  CH.sub.3                                                                          CH.sub.3                                                                          4-FC.sub.6 H.sub.4                                                                      H   C.sub.6 H.sub.5                                                                     C  41.91                                                                             C 42.02                                                                             91-92                                                               H   3.06                                                                             H  3.12                                                                  N   8.50                                                                             N  8.52                                                                  Br 36.37                                                                             Br                                                                               36.41                                                                  F   2.88                                                                             F  2.93                                       4  CH.sub.3                                                                          CH.sub.3                                                                           ##STR246##                                                                             H   C.sub.6 H.sub.5                                                                     C H N Br                                                                          42.88  4.07 10.87 37.21                                                           C H N Br                                                                         43.12  4.11 10.91 36.89                                                           122- 124                                 5  CH.sub.3                                                                          CH.sub.3                                                                           ##STR247##                                                                             H   C.sub.6 H.sub.5                                                                     C H N Br                                                                          43.90  4.01  8.09 38.10                                                           C H  N Br                                                                        43.94  4.14  8.84 37.96                                                           153- 154                                 6  CH.sub.3                                                                          CH.sub.3                                                                          C.sub.6 H.sub.5                                                                         CH.sub.3                                                                           C.sub.6 H.sub.5                                                                     C  45.24                                                                             C 45.48                                                                             146-                                                                H   3.32                                                                             H  3.41                                                                             148                                                                 N   8.79                                                                             N  8.93                                       7  C.sub.2 H.sub.5                                                                   CH.sub.3                                                                          C.sub.6 H.sub.5                                                                         H   C.sub.6 H.sub.5 139-                                                                           140                                                                            (dec)                                    8  CH.sub.3                                                                          CH.sub.3                                                                          p-ClC.sub.6 H.sub.4                                                                     H   C.sub.6 H.sub.5                                          9  CH.sub.3                                                                          CH.sub.3                                                                           ##STR248##                                                                             H   C.sub.6 H.sub.5                                          10 CH.sub.3                                                                          CH.sub.3                                                                           ##STR249##                                                                             H   C.sub.6 H.sub.5                                          11 CH.sub.3                                                                          CH.sub.3                                                                           ##STR250##                                                                             H   C.sub.6 H.sub.5                                          12 CH.sub.3                                                                          CH.sub.3                                                                           ##STR251##                                                                             H   C.sub.6 H.sub.5                                          13 CH.sub.3                                                                          CH.sub.3                                                                           ##STR252##                                                                             H   C.sub.6 H.sub.5                                          14 CH.sub.3                                                                          CH.sub.3                                                                           ##STR253##                                                                             H   C.sub.6 H.sub.5                                          15 CH.sub.3                                                                          CH.sub.3                                                                          C.sub.6 H.sub.5                                                                         F   C.sub.6 H.sub.5                                          16 CH.sub.3                                                                          CH.sub.3                                                                          C.sub.6 H.sub.5                                                                         Cl  C.sub.6 H.sub.5                                          17 CH.sub.3                                                                          CH.sub.3                                                                          C.sub.6 H.sub.5                                                                         Br  C.sub.6 H.sub.5                                          18 CH.sub.3                                                                          CH.sub.3                                                                           ##STR254##                                                                             H                                                                                   ##STR255##                                              19 CH.sub.3                                                                          CH.sub.3                                                                           ##STR256##                                                                             H   C.sub.6 H.sub.5                                          20 CH.sub.3                                                                          CH.sub.3                                                                          H        H   H                                                        21 CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3 CH.sub.3                                                                           CH.sub.3                                                 22 CH.sub.3                                                                          CH.sub.3                                                                          Cl       H                                                                                   ##STR257##                                              23 CH.sub.3                                                                          CH.sub.3                                                                          Br       Br  Br                                                       __________________________________________________________________________

                                      TABLE Ik                                     __________________________________________________________________________     Pyraislium salts of formula                                                     ##STR258##                                                                                               Analysis   M.P.                                     No R.sub.2                                                                           R.sub.3                                                                             R.sub.4 R.sub.5                                                                          R.sub.6                                                                              Calculated                                                                           Found                                                                               °C.                                                                           Method                             __________________________________________________________________________     1  Br      Br        SO.sub.2 C.sub.6 H.sub.5                                                                        63-75                                                                          (dec)                                    2  Cl Cl                              122-123                                  3  C.sub.2 H.sub.5   CH(CH.sub.3).sub.2                                                                   C 72.23                                                                              C 72.03                                                                             hygro-                                                                               A                                                             H  7.14                                                                              H  7.41                                                                             scopic                                                              N 12.03                                                                              N 11.61                                                                             gum                                      4  CH.sub.3          CH(CH.sub.3).sub.2                                                                   C 69.06                                                                              C 69.37                                                                             hygro-                                                                               A                                                             H  7.08                                                                              H  7.09                                                                             scopic                                                              N 11.93                                                                              N 11.67                                                                             gum                                      5  CH.sub.3          C(CH.sub.3).sub.3                                                                    C 69.54                                                                              C 69.58                                                                             hygro-                                                                               A                                                             H  7.29                                                                              H  6.81                                                                             scopic                                                              N 11.58                                                                              N 11.74                                                                             gum                                      6  Cl      I         Cl               128-131                                                                              A                                                                        (dec)                                    7  Br CH.sub.3                                                                            Br        Br               180-182                                                                              A                                                                        (dec)                                    8  Br      OCF.sub.3 Br               gum                                      9  Br      SO.sub.2 C.sub.6 H.sub.5                                                                 Br               110-115                                  10 Br      COCH.sub.3                                                                               Br               143-144                                                                              A                                  11 Br      Br        COCH.sub.3       129-129-5                                12 Br Cl   CH.sub.3  Br               143-144                                  13 Br      Br      Cl                                                                               Br               175- 176                                 14 I       CH.sub.3  CH.sub.3         142.5-144                                15 Br CH.sub.3                                                                            CH.sub.3  Br               156-157                                                                        (dec)                                    16 Br Cl   Br        Cl               193                                                                            (dec)                                    17 Br      F         F                111-114                                  18 Br      CN        Br               62                                       19 CH.sub.3                                                                          CH.sub.3       Br               123.5-126.5                              20 Cl Cl             Br               118-129                                  21 Br Br             Br                                                        22 Br Br           Br                                                                               Br               164-164.5                                23 Br                C.sub.2 H.sub.5                                                                      C 59.77                                                                              C 59.86                                                                             hygro-                                                              H  5.22                                                                              H  5.14                                                                             scopic                                                              N 11.15                                                                              N 11.12                                                                             gum                                      24 C.sub.2 H.sub.5                                                                                   ##STR259##      hygro- scopic gum                        25 CH.sub.3                                                                               Br        CH.sub.3                                                                             C 57.70                                                                              C 57.38                                                                             hygro-                                                              H  5.42                                                                              H  5.13                                                                             scopic                                                              N 10.77                                                                              N 10.49                                                                             gum                                      26 Br F    Br        Br               175-179                                                                        (dec)                                    27 CH.sub.3          CH.sub.3         143-145                                                                              A                                  28 Br      CH.sub.3  Br               178-179                                                                              A                                  29 C.sub.2 H.sub.5   C.sub.2 H.sub.5                                                                      C 70.41                                                                              C 70.41                                                                             gum   A                                                             H  7.00                                                                              H  7.14                                                                  N 12.17                                                                              N 12.10                                       30 Br                                 109-110.5                                31 Br                Br               130-132.5                                                                            B                                  32 Br      SO.sub.2 N(CH.sub.3).sub.2                                                               Br               65-78                                    33 Br      SO.sub.2 OCH.sub.2 C.sub.6 H.sub.5                                                       Br                                                        34 Br                                                                                      ##STR260##                                                                              Br                                                        35 Br      NHCOCH.sub.3                                                                             Br               173-179                                  36 Br Br                                                                       37 Br SO.sub.2 CH.sub.3                                                                   Br        Br                                                        38 Br                I                                                         39 I                 I                                                         40 Br                CH.sub.3                                                  41 I                 CH.sub.3                                                  42 F                 Br                                                        43 F                 F                                                         44 F                 I                                                         45 Cl                I                                                         46 Cl                Br               gum                                      47 Br                CH(CH.sub.3).sub.2                                        48 Br              Br                 95-97                                    49         SO.sub.2 CH.sub.3          108-110                                  50 Br      Br        SO.sub.2 C.sub.4 H.sub.9                                  51 I  I            I                                                           52 Br Br           Br                 gum                                      53 Br      SO.sub.2 CH.sub.3          77-84                                                                          (dec)                                    54 C.sub.2 H.sub.5                                                                        Br        C.sub.2 H.sub.5  104-105                                  55 Br      CH.sub.3  CH.sub.3         133-135                                  56 Cl      I         I                180-182                                                                        (dec)                                    57 Br      I         I                129-131                                  58 I       I         I                148-150                                                                        (dec)                                    __________________________________________________________________________

                  TABLE Il                                                         ______________________________________                                         Salts of Formula:                                                               ##STR261##                                                                    R.sub.2      R.sub.4   R.sub.6   M.P.                                          ______________________________________                                         Br           Br        Br        89-92                                         ______________________________________                                    

                  TABLE Im                                                         ______________________________________                                         Salts of Formula:                                                               ##STR262##                                                                    R.sub.2     R.sub.4   R.sub.6   M.P.                                           ______________________________________                                         Br          Br        Br        150-152                                        ______________________________________                                    

                  TABLE Io                                                         ______________________________________                                         Salts of Formula:                                                               ##STR263##                                                                                 Analysis     M.P.                                                 No   R.sub.2                                                                               R.sub.4                                                                               R.sub.6                                                                              Calculated                                                                             Found  (°C.)                           ______________________________________                                         1    CF.sub.3                                                                              Br     Br    C   45.86 C   46.16                                                                               126-127                                                     H   3.36  H   3.19 (dec)                                                       N   8.89  N   9.01                                                             F   9.04  F   9.23                                    2    Br     CF.sub.3                                                                              Br    C   47.08 C   47.24                                                                               140-142                                                     H   3.13  H   3.20 (dec)                                                       N   9.15  N   9.08                                                             F   9.31  F   9.46                                                             Br  26.11 Br  26.11                                   3    Cl     Cl     Cl    C   55.39 C   55.69                                                                               105-106                                                     H   4.04  H   3.92                                                             N   11.23 N   11.02                                   4    I      Br     Br    C   41.22 C   41.51                                                                               142-143                                                     H   2.86  H   3.00 (dec)                                                       N   8.36  N   8.35                                                             Br  23.85 Br  23.56                                   5    CH.sub.3                                                                              CH.sub.3                                                                              CH.sub.3                                                                             C   69.55 C   69.19                                                                               88-91                                                       H   6.86  H   6.83 (dec)                                                       N   12.30 N   12.06                                   6    Br     Cl     Br    C   47.73 C   47.51                                                                               128-132                                                     H   3.31  H   3.35                                                             N   9.68  N   9.66                                    ______________________________________                                    

EXAMPLE 2 Preparation of 2,4,6-tribromo-N-nitro-N-(2-propynyl) aniline

2,4,6-tribromo-N-nitroaniline (5.0 g; 0.01334 mol) is reacted with a methanolic solution of sodium hydroxide (0.53 g; 0.01324 mol) in the presence of methanol (60 ml). The solvent is then removed, and the residue dried. The thus obtained sodium salt is dissolved in dimethyl sulfoxide (DMSO) and reacted with 3-bromopropyne (1.52 g; 0.0147 mol) at 25° C. The reaction mixture is stirred 16 hours and then poured into water. The title product is extracted with ether (3×125 ml), the combined extract washed with water, dilute sodium hydroxide, water and brine. The ethereal solution is then dried over magnesium sulfate and the solution concentrated to afford the product, mp. 58°-58.5° C.

By the above method, a number of N-substituted phenylnitramines are prepared. These are listed in Table II below.

                  TABLE II                                                         ______________________________________                                         Nsubstituted phenylnitramines                                                   ##STR264##                                                                                                               M.P.                                No  R.sub.1       R.sub.2 R.sub.3                                                                         R.sub.4                                                                               R.sub.5                                                                            R.sub.6                                                                             °C.                          ______________________________________                                         1   CH.sub.2 CHCH.sub.2                                                                          Br       Br         Br   oil                                      ##STR265##   Br       Br         Br   153- 156                            3   CH.sub.2 CO.sub.2 CH.sub.3                                                                   Br       Br         Br   122                                 4   CH.sub.2 CH.sub.2 CO.sub.2 CH.sub.3                                                          Br       Br         Br   82-                                                                            83                                  5   CH.sub.2 CCH  Br                  Br   75-                                                                            77                                  6   CH.sub.2 CN   Br       Br         Br   85-                                                                            87                                  7                                                                                   ##STR266##   Br       Br         Br   135- 138                            8   CH.sub.2 C.sub.6 H.sub.5                                                                     Br                  Br   84-                                                                            86                                  9   CH.sub.2 C.sub.6 H.sub.5                                                                     Br       Br         Br   72-                                                                            73                                  10  CH.sub.3      Br                  Br   125-                                                                           127                                 11  CH(C.sub.2 H.sub.5).sub.2                                                                    NO.sub.2 CH.sub.3                                                                       CH(CH).sub.2                                                                              NO.sub.2                                                                            126-                                                                           126.5                               12  CH(C.sub.2 H.sub.5).sub.2                                                                    NO.sub.2 CH.sub.3                                                                       CH.sub.3   NO.sub.2                                                                            75.5-                                                                          77                                  13  CH.sub.3      Br       Br         Br   94.5-                                                                          95                                  14  n-C.sub.12 H.sub.25                                                                          Br       Br         Br   Liquid                              ______________________________________                                    

EXAMPLE 3 Preparation of (2-Propynyloxy) (2,4,6-tribromophenyl) diimide-1-oxide

A suspension of the silver salt of 2,4,6-tribromophenylnitramine (4.82 g; 0.01 mol) in ether is reacted with 3-bromopropyne (1.3 g; 0.011 mol) under a nitrogen atmosphere at 25° C. After 16 hours the mixture is filtered through a layer of celite, the ether solution is washed with water, dilute sodium hydroxide and again with water and then dried over anhydrous magnesium sulfate. The solvent is then removed under vacuum, the residue dissolved in methylene chloride and filtered through a layer of alumina. The filtrate is concentrated and crystallized from petroleum ether. Thin layer chromatography (silica gel; hexane:CH₂ Cl₂ in a 1:1 ratio) and NMR indicate the product to be a 83 to 17 percent mixture of the O and N substituted products. ##STR267##

Substituting methyl iodide or n-dodecyl bromide for 3-bromopropyne-1 in the above reaction, the corresponding O-methyl and O-n-dodecyl analogs are obtained, respectively.

Similarly reacting the silver salt of 2,6-dibromophenylnitramine with methyl iodide affords the corresponding O-methyl compound.

EXAMPLE 4 Preparation of substituted benzylnitramines

A solution of the appropriate benzyl halide or mesylate (0.03 mol) and ammonium nitrourethane in dry dimethylformamide (50 ml) is heated at 80° C. for four hours. The reaction mixture is cooled and poured into ice water, and then extracted three times with ether. The combined extracts are washed with water and dried over anhydrous magnesium sulfate. Next, anhydrous ammonia gas is passed into the solution for 30 minutes. The precipitated material is isolated, washed in the ether and then dissolved in water (100 ml). The aqueous solution is stirred vigorously and its pH adjusted to 5. The precipitated product is filtered, washed with water and dried. If desired, the product may be recrystallized from a mixture of hexane:toluene (1:1).

The thus prepared products are shown in Table III below.

                  TABLE III                                                        ______________________________________                                          ##STR268##                                                                                                            M.P.                                   No    R.sub.2 R.sub.3                                                                               R.sub.4                                                                             R.sub.6                                                                              R.sub.1 °C.                             ______________________________________                                         1     Cl      H      H    Cl    H         121-122.5                            2     H       H      Cl   H     H       90-91                                  3     Cl      Cl     H    Cl    H       71-72                                  4     CH.sub.3                                                                               H      H    CH.sub.3                                                                             H       93                                     5     CL      H      H    Cl    CH.sub.3                                                                                99-101                                6     Cl      H      Cl   H     H       72-75                                  7     CF.sub.3                                                                               H      H    Br    H                                              8     Br      H      H    Br    H                                              9     Br      H      H    Cl    H                                              10    F       H      H    F     H                                              11    Br      H      H    Br    CH.sub.3                                       12    CF.sub.3                                                                               H      H    Br    CH.sub.3                                       13    Br      H      H    Br    F                                              14    Br      H      H    Br    CF.sub.3                                       15    Br      H      H    Br    C.sub.6 H.sub.5                                16    Cl      H      H    Cl    CF.sub.3                                       17    Cl      H      H    Cl    CN                                             18    Cl      H      H    Cl    CN                                             19    Cl      H      H    Cl    SO.sub.2 CH.sub.3                              ______________________________________                                    

EXAMPLE 5 Preparation of Miscellaneous Salts of Substituted Benzylnitramines

By the methods of Example 1, a number of salts of various benzylnitramines are prepared. These are shown in Table IV below.

                                      TABLE IV                                     __________________________________________________________________________      ##STR269##                                                                                                      M.P.                                         No R.sub.2                                                                            R.sub.3                                                                           R.sub.4                                                                           R.sub.6                                                                            R.sub.1                                                                           X.sup.+       °C.                                   __________________________________________________________________________     1  CH.sub.3                                                                           H  H  CH.sub.3                                                                           H                                                                                  ##STR270##   93-93                                        2  Cl  H  Cl H   H                                                                                  ##STR271##   120-122                                      3  Cl  H  H  Cl  CH.sub.3                                                                           ##STR272##   165-172                                      4  H   H  Cl H   H                                                                                  ##STR273##   103-125                                      5  Cl  H  H  Cl  H                                                                                  ##STR274##                                                6  Cl  H  H  Cl  H                                                                                  ##STR275##   >260                                         7  Cl  H  H  Cl  CH.sub.3                                                                           ##STR276##   >300                                         8  Cl  H  H  Cl  CH.sub.3                                                                          NH.sub.4.sup.+                                             9  Br  H  H  Br  H                                                                                  ##STR277##                                                10 Cl  H  H  Cl  CF.sub.3                                                                           ##STR278##                                                11 Cl  H  H  Cl  CH.sub.3                                                                           ##STR279##                                                12 Cl  H  H  Cl  H                                                                                  ##STR280##                                                13 Cl  H  H  Cl  H                                                                                  ##STR281##                                                14 Br  H  H  Br  CH.sub.3                                                                          Na.sup.+                                                   15 Br  H  H  CF.sub.3                                                                           H                                                                                  ##STR282##                                                __________________________________________________________________________

EXAMPLE 6 Lithium diisopopylamide mediated N-nitration of anilines

A solution of diisopropylamine (0.20 mol) in diethylether (300 ml) is cooled to -75° C. under N₂ and lithiated with n-butyllithium (0.20 ml of a 1.6 M solution hexane). The solution is allowed to warm slowly to 0° C. over four hours, then is cooled down to -60° C. A solution of the appropriate aniline (0.10 mol) in ether (300 ml) is added dropwise and the reaction mixture is allowed to warm to 0° C. over one hour. Cooling the reaction mixture back to -60° C. is followed by the addition (dropwise) of methyl nitrate (0.10 mol). The reaction mixture is allowed to warm to ambient temperature overnight, and poured onto 300 ml water. The aqueous layer is washed with ether, cooled in an ice bath, and acidified dropwise with concentrated hydrochloric acid. The mixture is extracted with ether, the combined ether extracts are washed successively with cold 5% HCl, water and brine. Removal of the solvent under vacuum affords the product.

By the above method and other methods known in the art, a number of N-nitroanilines are prepared, and are shown in Table V below.

                                      TABLE V                                      __________________________________________________________________________      ##STR283##                                                                                                   M.P.                                            No R.sub.2                                                                              R.sub.3                                                                              R.sub.4                                                                               R.sub.5                                                                           R.sub.6                                                                              °C.                                      __________________________________________________________________________     1  Br          Br     Cl CH.sub.3                                                                             140 (dec)                                       2  CH.sub.3                                                                             CH.sub.3        Br    94-94.5                                         3  CH.sub.3    CH.sub.3  I     93-98                                           4  Br          Br        SO.sub.2 C.sub.6 H.sub.5                                                             116-117                                         5  Br    Cl    CH.sub.3  Br    137.5-138                                       6  Br    Cl    Br        Cl    126 (dec)                                       7  Br    CH.sub.3                                                                             CH.sub.3  Br    123.5-124                                       8  Br          COC.sub.6 H.sub.5                                                                        Br    134.5-135                                       9  Br          CN        Br    139-139.5                                       10 Br    Br           Br Br    140-154 (dec)                                   11 C.sub.2 H.sub.5                                                                            Br        CH(CH.sub.3).sub.2                                                                   113-115 (dec)                                   12 C.sub.2 H.sub.5                                                                            Br                                                                                        ##STR284##                                                                          118-122 (dec)                                   13 Br          Br        C.sub.2 H.sub.5                                                                      92-98                                           14 Cl          Cl        I     119-122                                         15 Br          Br        CH.sub.3                                                                             106-108                                         16 CH(CH.sub.3).sub.2                                                                         Br        CH.sub.3                                                                             70-80                                           17 Br          C.sub.2 H.sub.5                                                                          Br    66-80                                           18 Br                    C.sub.2 H.sub.5                                                                      40-50                                           19 CH.sub.3    Br        C(CH.sub.3).sub.3                                                                    85-90                                           20 C.sub.2 H.sub.5                                                                                       ##STR285##                                                                          gum                                             21 Br    F     Br        Br    128-129                                         22 Cl          Cl        I     120-122                                         23 Br          CH.sub.3  Br    122-123                                         24 Br                          61-62                                           25 CF.sub.3           Br       75-77                                           26 Br                    Br    108-111 (dec)                                   27 CH.sub.3              CH.sub.3                                                                             104.5-105 (dec)                                 28 Cl    Cl                    58-60                                           29 CH.sub.3    Br        CH.sub.3                                                                             127.5-129                                       30 CH.sub.3              C(CH.sub.3).sub.3                                                                    oil                                             31 CH.sub.3              CH(CH.sub.3).sub.2                                                                   oil                                             32 C.sub.2 H.sub.5       CH(CH.sub.3).sub.2                                    33 C.sub.2 H.sub.5       C.sub.2 H.sub.5                                                                      71.5-73.5                                       34 Br                 Br       94-95.5                                         35 I     I            I                                                        36 Br    Br           Br       112.5-114 (dec)                                 37 Br    Br              Br                                                    38 Cl    Cl    Br              98-100                                          39 Cl    Cl              Br    84-86                                           40 CH.sub.3                                                                                    ##STR286##                                                     41 Br                                                                                          ##STR287##                                                     42 Br          SO.sub.3 CH.sub.2 C.sub.6 H.sub.5                                                        Br                                                    43 Br    NHCOCH.sub.3                                                                         Br        Br                                                    44 CF.sub.3              Br                                                    45 Br                    I                                                     46 I                     I                                                     47 I                     Cl                                                    48 I                     Br                                                    49 I           I         I     140-141.5                                       50 Br          Br        C.sub.4 H.sub.9 SO.sub.2                                                             137 (dec)                                       51 Br          CH.sub.3 SO.sub.2                                                                        Br    161-161.5                                       52 Br          CH.sub.3 CO                                                                              Br    124-124.5                                       53 CH.sub.3 CO Br        Br                                                    54 Br          SO.sub.2 N(CH.sub.3).sub.2                                                               Br    143-144                                         55 Br          NHCOCH.sub.3                                                                             Br    168 (dec)                                       56                                                                                             ##STR288##     183-184 (dec)                                   57 Br                                                                                          ##STR289##                                                                              Br                                                    58 Br                                                                                          ##STR290##                                                                              Br    145 (dec)                                       59 C.sub.2 H.sub.5                                                                            Br        C.sub.2 H.sub.5                                                                      66-67                                           60 Br          I         I     118.5-121                                       61 Br          CH.sub.3  CH.sub.3                                                                             103-105                                         62 Cl          I         I     118-119                                         63 CH.sub.3 S  Br        Br                                                    __________________________________________________________________________

EXAMPLE 7 Evaluation of 2,4,6-trisubstituted-N-nitroaniline salts as Dwarfing and Stem Stiffening agents for Barley

In the following tests, test compounds are dissolved or dispersed in acetone-water (1:1) mixtures at the final concentration corresponding to the kg/ha rates indicated in the table below. The solution also contains 0.25% v/v colloidal BIOFILM® (a product of Colloidal Products Corp.) which is a mixture of alkyl aryl polyethoxyethanol, free and combined fatty acids, glycol ethers, dialkylbenzene carboxylate and 2-propanol.

The plant species used in these tests are barley (Hordeum vulgare), (Mexico) and soybean (Glycine max)Adelphia.

The solution or dispersion of the compound under test is sprayed at a rate of 747 l/ha with a moving nozzle along an overhead stationary track. The spray nozzle moves at a constant speed over the plants.

The plants are grown in plastic pots, and are well established at the time of treatment. The seedlings of barley are 10 to 20 cm in height, while the seedlings of soybeans are at the second to third trifoliate stage. Plants are watered prior to treatment and then sprayed to provide the kg/ha rate of test compound desired. After spraying the plants are placed on greenhouse benches and watered and fertilized in accordance with normal greenhouse procedures.

Three weeks after spraying the plants are measured and harvested. Harvesting is done at the boot stage. All treatments are replicated six times and comparisons are made against untreated controls. Data obtained are reported in Table VI below as percent reduction in plant height over untreated controls.

                  TABLE VI                                                         ______________________________________                                         Evaluation of test compounds as                                                Barley dwarfing agents                                                                                    % Reduction in                                                                 Plant Height                                                           Rate    over untreated                                      Compound           kg/ha   controls                                            ______________________________________                                         1,2-Dimethyl-3,5-diphenyl-                                                                        1.5     15                                                  pyrazolium salt with                                                                              0.50    8.7                                                 2,4,6-tribromo-N--aci-                                                                            0.17    37.8                                                nitroaniline                                                                   4-Methoxy-1,2-dimethyl-3,5-                                                                       2.24    >60                                                 diphenylpyrazolium salt with                                                                      0.56    >20 <35                                             2,4,6-tribromo-N--aci-                                                                            0.11    >10 <15                                             nitroaniline                                                                   ______________________________________                                    

                  TABLE VIa                                                        ______________________________________                                         Evaluation of test compounds for Dwarfing of Barley                                                        % Reduction in                                                         Kg/ha   Plant Height over                                  Compound            Rate    untreated controls                                 ______________________________________                                         2,4,6-Tribromo-N--  1.5     2.0                                                nitroaniline, potassium                                                                            0.50    11.8                                               salt                0.17    2.7                                                2,4,6-Tribromo-N--  1.5     13.0                                               nitroaniline, sodium                                                                               0.50    13.0                                               salt 0.17           6.2                                                        2,4,6-Tribromo-N--  1.5     11.1                                               nitroaniline with   0.50    13.0                                               octylamine (1:1)    0.17    10.5                                               2,4,6-Tribromo-N--nitro-                                                                           1.5     15.3                                               aniline with ammonia (1:1)                                                                         0.50    16.3                                               2,4,6-Tribromo-N--nitroaniline                                                                     1.5     15.8                                               tetrabutyl, ammonium salt                                                                          0.50    --                                                                     0.17    10.5                                               (2-Chloroethyl)trimethyl                                                                           1.5     28.1                                               ammonium salt with 2,4,6-                                                                          0.50    16.5                                               tribromo-N--aci-nitroaniline                                                                       0.17    23.1                                               2,4,6-Tribromo-N--nitro-                                                                           2.24    >50                                                aniline with methylamine (1:1)                                                                     0.56    >50                                                                    0.11     10                                                4-Methoxy-1,2-dimethyl-3,5-                                                                        2.24    >60                                                diphenylpyrazolium salt with                                                                       0.56    >20 <35                                            2,4,6-tribromo-N--aci-                                                                             0.11    >10 <15                                            nitroaniline                                                                   2,4,6-Tribromo-N--nitro-                                                                           2.0     >10 <15                                            aniline, magnesium salt                                                                            1.0     >10 <15                                                                0.5     >10 <15                                            2,4,6-Tribromo-N--nitro-                                                                           2.0     >10 <15                                            aniline, Calcium salt                                                                              1.0     >10 <15                                                                0.5     >10 <15                                            ______________________________________                                    

                  TABLE VIb                                                        ______________________________________                                         Evaluation of test compounds as Dwarfing agents                                and stem stiffening agents for soybeans                                                                    % Reduction in                                                         Rate    Plant Height over                                  Compound            Kg/ha   untreated controls                                 ______________________________________                                         2,4,6-Tribromo-N--nitro-                                                                           0.25    >40                                                aniline, sodium salt                                                                               0.125   >35                                                2,4,6-Tribromo-N--nitro-                                                                           0.50    >30                                                aniline, potassium salt                                                                            0.25    >5                                                                     0.125   >5                                                 2,4,6-Tribromo-N--nitro-                                                                           2.0     >10 <15                                            aniline, magnesium salt                                                                            1.0     >10 <15                                                                0.5     >20 <35                                            2,4,6-Tribromo-N--nitro-                                                                           2.0     >10 <15                                            aniline, calcium salt                                                                              1.0     >10 <15                                                                0.5     >10 <15                                            2,4,6-Tribromo-N--nitro-                                                                           2.0     >60                                                aniline with ammonia (1:1)                                                                         0.5     >60                                                                    0.1     >10 <15                                            2,4,6-Tribromo-N--nitro-                                                                           2.0     >60                                                aniline with methylamine                                                                           0.5     >60                                                (1:1)               0.1     >10 <15                                            (2-Chloroethyl)trimethyl                                                                           2.0     >60                                                ammonium salt with 2,4,6-                                                                          0.5     >60                                                Tribromo-N--aci-nitroaniline                                                                       0.1     normal                                             Tetrabutylammonium salt with                                                                       0.5     >50                                                2,4,6-tribromo-N--nitro-                                                                           0.25    >35                                                aniline             0.125   >25                                                Benzyltriethylammonium salt                                                                        0.5     >50                                                with 2,4,6-tribromo-N--aci-                                                                        0.25    >35                                                nitroaniline        0.125   >25                                                1-Hexadecylpyridinium                                                                              0.5     >50                                                salt with 2,4,6-tribromo-                                                                          0.25    >35                                                N-- aci-nitroaniline                                                                               0.125   >35                                                1,1-Dimethylpiperidinium                                                                           0.5     >50                                                salt with 2,4,6-tribromo-N--                                                                       0.25    >35                                                aci-nitroaniline    0.125   >25                                                Dibenzylamine(1:1)with 2,4,6-                                                                      0.5     >50                                                tribromo-N--nitroaniline                                                                           0.25    >35                                                                    0.125   >25                                                Dodecylamine with 2,4,6-                                                                           0.5     >35                                                tribromo-N--nitroaniline                                                                           0.25    >25                                                                    0.125   >15                                                Methyltriphenyl phosphonium                                                                        0.5     >50                                                salt with 2,4,6-tribromo-                                                                          0.25    >35                                                N--aci-nitroaniline 0.125   >25                                                Tributyl(2,4-dichloro-                                                                             0.5     >50                                                benzyl)phosphonium salt with                                                                       0.25    >25                                                aniline             0.125   >8                                                 1,2-Dimethyl-3,5,diphenyl-                                                                         0.5     >20 <35                                            pyrazolium salt with 2,4,6-                                                                        0.25    >10 <15                                            tribromo-N--aci-nitroaniline                                                                       0.125   normal                                             4-Methoxy-1,2-dimethyl-3,5-                                                                        0.5     >35                                                diphenylpyrazolium salt                                                                            0.25    >35                                                with 2,4,6-tribromo-N--aci-                                                                        0.125   >10                                                nitroaniline                                                                   3-(p-Fluorophenyl)-1,2-                                                                            0.5     >25                                                dimethyl-5-phenylpyrazolium                                                                        0.25    >25                                                salt with 2,4,6-tribromo-N--                                                                       0.125   >20                                                aci-nitroaniline                                                               1,2-Dimethyl-3-(methylpiperi-                                                                      0.5     >25                                                dino)-5-phenylpyrazolium salt                                                                      0.25    >25                                                with 2,4,6-tribromo-N--aci-                                                                        0.125   >20                                                nitroaniline                                                                   1,2-Dimethyl-3,5-diphenyl-                                                                         0.5     >40                                                pyrazolium salt with 4,6-                                                                          0.25    >40                                                dibromo-α,α,α-trifluoro-N--                                                      0.125   >20                                                aci-nitro-o-toluidine                                                          1,2-Dimethyl-3,5-diphenyl-                                                                         0.5     >20                                                pyrazolium salt with 2,6-                                                                          0.25    >15                                                dibromo-α,α,α-trifluoro-N--                                                      0.125   >10                                                aci-nitro-o-toluidine                                                          1,2-Dimethyl-3,5-diphenyl-                                                                         0.5     >25                                                pyrazolium salt with 2,4,6-                                                                        0.25    >15                                                trichloro-N--aci-nitro-                                                                            0.125   >10                                                aniline                                                                        1,2-Dimethyl-3,5-diphenyl-                                                                         0.5     >25                                                pyrazolium salt with 2,4-                                                                          0.25    >15                                                dibromo-6-iodo-N--aci-                                                                             0.125   >10                                                nitroaniline                                                                   cis-1,2-Dimethyl-3,5-diphenyl-                                                                     0.5     >60                                                pyrazolidinium salt with                                                                           0.25    >30                                                2,4,6-tribromo-N--nitroaniline                                                                     0.125   >20                                                1,2-Dimethyl-3,5-diphenyl-                                                                         0.5     >10                                                pyrazolium salt with 2,4,6-                                                                        0.25    >5                                                 Trimethyl-N--aci-nitroaniline                                                                      0.125   slight increase                                    3-Cyclohexyl-1,2-dimethyl-5-                                                                       0.5     >40                                                phenylpyrazolium salt with                                                                         0.25    >20                                                2,4,6-tribromo-N--aci-nitro-                                                                       0.125   >10                                                aniline                                                                        1,2-Dimethyl-3,5-diphenyl-                                                                         0.5     >40                                                pyrazolium salt with 2,6-                                                                          0.25    >30                                                dibromo-4-chloro-N--aci-                                                                           0.125   >25                                                nitroaniline                                                                   ______________________________________                                    

EXAMPLE 8 Evaluation of test compounds for Increasing axillary Branching and improving the canopy of Broad leaf plants using Soybeans (Glycine max) Adelphia variety as the plant species

In these tests seedling soybean plants approximately three weeks old, and grown in plastic pots to the 2nd to 3rd trifoliate stage, are sprayed with solutions or dispersions of test compound prepared as described in Example 7 above. The same spraying apparatus, described in Example 7 above, is used and after spraying the plants are placed on greenhouse benches and watered and fertilized. Three weeks after treatment the plants are examined to determine what effect the application of test compound has had on the axillary branching and canopy development of the treated plants.

Increased axillary branching and improved canopy are biological responses which are highly advantageous in the growing of ornamental plants. These responses also have advantage in many crops since increased branching may result in the greater production of fruit, while improved canopy tends to shade and suppress the growth of undesirable weeds that compete with the crops for sunlight, water and plant nutrients. Data obtained are reported in table VII below where axillary branching and canopy are reported as percent increase over untreated controls.

                                      TABLE VII                                    __________________________________________________________________________     Evaluation of test compounds for increasing axillary branching and             improving the                                                                  canopy of treated broad leaf plants using soybeans                             (var. Adelphia) as the plant species                                                                 % Increase in                                                                              % Increase in                                                  Rate                                                                               axillary branching                                                                         Plant Canopy over                            Compound          kg/ha                                                                              over untreated controls                                                                    untreated controls                           __________________________________________________________________________     1,2-Dimethyl-3,5-diphenyl-                                                                       0.5 >10 <15     >10 <15                                      pyrazolium salt with 2,4,6-                                                                      0.25                                                                               >10 <15     >20 <35                                      tribromo-N--aci nitroaniline                                                                     0.125                                                                              >10 <15     >10 <15                                      4-Methoxy-1,2-dimethyl-3,5-                                                                      0.5 >10 <15     >20 <35                                      diphenylpyrazolium salt with                                                                     0.25                                                                               normal      >20 <35                                      2,4,6-Tribromo-N--aci-nitroaniline                                                               0.125                                                                              normal      normal                                       3-(p-Fluorophenyl)-1,2-dimethyl-3,5-                                                             0.5 normal      >10 <15                                      diphenylpyrazolium salt with                                                                     0.25                                                                               >10 <15     >10 <15                                      2,4,6-tribromo-N--aci-nitroaniline                                                               0.125                                                                              normal      normal                                       1,2-Dimethyl-3,5-diphenylpyrazolium                                                              0.5 >10 <15     >10 <15                                      salt with 4,6-dibromo-α,α,α-tri-                                               0.25                                                                               >10 <15     >10 <15                                      fluoro-N--aci-o-toluidine                                                                        0.125                                                                              >10 <15     >20 <35                                      1,2-Dimethyl-3,5-diphenylpyrazolium                                                              0.5 >20 <35     >20 <35                                      salt with 2,4-dibromo-6-iodo-N--                                                                 0.25                                                                               >20 <35     >20 <35                                      aci-nitroaniline  0.125                                                                              >10 <15     >10 <15                                      1,2-Dimethyl-3,5-diphenylpyrazolium                                                              0.5 >10 <15     >10 <15                                      salt with 2,4,6-trimethyl-N--aci-                                                                0.25                                                                               >10 <15     >10 <15                                      nitroaniline      0.125                                                                              normal      normal                                       3-Cyclohexyl-1,2-dimethyl-                                                                       0.5 >10 <15     slight reduction                             5-phenylpyrazolium salt                                                                          0.25                                                                               >10 <15     >10 <15                                      with 2,4,6-tribromo-N--                                                                          0.125                                                                              >10 <15     >10 <15                                      aci-nitroaniline                                                               1,2-Dimethyl-3,5-diphenyl-                                                                       0.5 >10 <15     >10 <15                                      pyrazolium salt with 2,6-                                                                        0.25                                                                               >10 <15     >10 <15                                      dibromo-4-chloro-N--aci-                                                                         0.125                                                                              >10 <15     normal                                       nitroaniline                                                                   2,4,6-Tribromo-N--nitroaniline,                                                                  0.50                                                                               >20 <35     >10 <15                                      sodium salt       0.25                                                                               >20 <35     >20 <35                                                        0.125                                                                              >20 <35     >20 <35                                      2,4,6-Tribromo-N--nitroaniline,                                                                  0.50                                                                               >20 <35     normal                                       potassium salt    0.25                                                                               normal      >10 <15                                                        0.125                                                                              normal      >10 <15                                      (2-chloroethyl)trimethyl                                                                         0.50                                                                               >20 <35     >20 <35                                      ammonium salt with 2,4,6-                                                                        0.25                                                                               >10 <15     >10 <15                                      tribromo-N--aci-nitroaniline                                                                     0.125                                                                              normal      >10 <15                                      2,4,6-tribromo-N--nitroaniline                                                                   0.50                                                                               >10 <15     Injury                                       with ammonia (1:1)                                                                               0.25                                                                               >10 < 15    >20 <35                                                        0.125                                                                              >20 <35     >20 <35                                      2,4,6-Tribromo-N--nitroaniline,                                                                  0.50                                                                               >10 <15     slight reduction                             diisopropylamine (1:1)salt                                                                       0.25                                                                               >10 <15     >10 <15                                                        0.125                                                                              >10 <15     >10 <15                                      2,4,6-Tribromo-N--nitroaniline,                                                                  0.50                                                                               >10 <15     slight reduction                             triethylamine (1:1)salt                                                                          0.25                                                                               >20 <35     slight reduction                                               0.125                                                                              normal      >10 <15                                      2,4,6-Tribromo-N--nitroaniline,                                                                  0.50                                                                               >10 <15     slight reduction                             octylamine salt   0.25                                                                               >10 <15     >10 <15                                                        0.125                                                                              normal      >10 <15                                      2,4,6-tribromo-N--nitroaniline,                                                                  0.50                                                                               >10 <15     >10 <15                                      tetrabutylammonium salt                                                                          0.25                                                                               >20 <35     >20 <35                                                        0.125                                                                              >20 <35     >20 <35                                      2,4,6-Tribromo-N--nitroaniline                                                                   0.5 >10 <15     >20 <35                                      with dibenzylamine                                                                               0.25                                                                               normal      >10 <15                                                        0.125                                                                              normal      normal                                       2,4,6-Tribromo-N--nitroaniline                                                                   0.5 >20 <35     >10 <15                                      with dodecylamine 0.25                                                                               >10 <15     >10 <15                                                        0.125                                                                              normal      normal                                       Benzyltriethyl ammonium salt                                                                     0.5 >10 <15     >10 <15                                      with 2,4,6-tribromo-N--aci-                                                                      0.25                                                                               normal      >10 <15                                      nitroaniline      0.125                                                                              normal      normal                                       1,1-Dimethylpiperidinium salt                                                                    0.5 >10 <15     >20 <35                                      with 2,4,6-tribromo-N--aci-                                                                      0.25                                                                               normal      >10 <15                                      nitroaniline      0.125                                                                              normal      normal                                       2,4,6-Tribromo-N--aci-nitro-                                                                     0.5 >20 <35     moderate reduction                           aniline calcium salt (2:1)                                                                       0.25                                                                               >20 <35     slight reduction                                               0.125                                                                              >20 <35     >10 <15                                      2,4,6-Tribromo-N--aci-nitro-                                                                     0.5 >20 <35     moderate reduction                           aniline, magnesium salt (2:1)                                                                    0.25                                                                               >20 <35     moderate reduction                                             0.125                                                                              >10 <15     >10 <15                                      2,4,6-Tribromo-N--nitro                                                                          0.5 >20 <35     moderate reduction                           aniline with cis 1,2-dimethyl-                                                                   0.25                                                                               >20 <35     moderate reduction                           3,5-diphenylpyrazolidine                                                                         0.125                                                                              >10 <15     >20 <35                                      Tributyl(2,4-dichlorobenzyl)                                                                     0.5 >20 <35     moderate reduction                           phosphonium salt with 2,4,6-                                                                     0.25                                                                               >10 <15     >10 <15                                      tribromo-N--aci-nitroaniline                                                                     0.125                                                                              normal      normal                                       1-Hexadecylpyridinium salt                                                                       0.5 normal      >10 <15                                      with 2,4,6-tribromo-N--aci-                                                                      0.25                                                                               normal      >10 <15                                      nitroaniline      0.125                                                                              normal      normal                                       Methyltriphenylphosphonium                                                                       0.5 >10 <15     >20 <35                                      salt with 2,4,6-tribromo-N--                                                                     0.25                                                                               normal      >10 <15                                      aci-nitroaniline  0.125                                                                              normal      normal                                       Methylamine salt with                                                                            0.5 normal      >10 <15                                      2,4,6-tribromo-N--aci-                                                                           0.25                                                                               normal      >10 < 15                                     nitroaniline      0.125                                                                              normal      normal                                       __________________________________________________________________________

EXAMPLE 9 Evaluation of Test Compounds To Determine Their Effectiveness for Increasing Flowering of Plants Using Soybeans (Glycine max) Var. Adelphia As The Plant Species

In the following tests seedling soybean plants growing in plastic cups are sprayed with aqueous-acetone solutions or dispersions of test compounds when they have reached the 2nd to 3rd trifoliate stage. Test solutions or dispersions are prepared with 0.25 v/v Colloidal BIOFILM® surfactant and sufficient test compound to provide the plants with 0.5, 0.25, 0.125 or 0.06 kg/ha of said compound when the test solutions are sprayed on said plants from an overhead sprayer delivering 747 l/ha of solution.

After spraying the plants are placed on greenhouse benches and watered and fertilized. Three weeks after spraying the plants are examined and the amount of flowering determined for all plants. Data obtained are reported in the table below as percent increase in flowering over untreated controls.

From the data reported in Table VIII below it can be seen that the compounds of the present invention applied at rates of from 0.06 to 0.25 kg/ha enhance flowering of treated plant more than 10% over untreated controls. This response is particularly desirable for treatment of flowering varieties of ornamental plants as well as agronomic crops.

                  TABLE VIII                                                       ______________________________________                                         Evaluation of test compounds to determine their                                effectiveness for increasing flowering                                         of the treated plants                                                                                       % Increase                                                                     in Flowering                                                           Rate    over untreated                                    Compound             kg/ha   controls                                          ______________________________________                                         1,2-Dimethyl-3,5-diphenyl-                                                                          0.25    >10 <15                                           pyrazolium salt with 2,4,6-                                                                         0.125   >20 <35                                           tribromo-N--aci-nitroaniline                                                                        0.06    >10 <15                                           4-Methoxy-1,2-dimethyl-3,5-                                                                         0.5     Moderate                                                                       Reduction                                         diphenylpyrazolium salt with                                                                        0.25    >10 <15                                           2,4,6-tribromo-N--aci-nitroaniline                                                                  0.125   >10 <15                                           1,2-Dimethyl-3-(3-methylpiperidino)-                                                                0.5     Slight                                                                         Reduction                                         5-phenyl salt with 2,4,6-tribromo-                                                                  0.25    >10 <15                                           N--aci-nitroaniline  0.125   >10 <15                                           1,2-Dimethyl-3,5-diphenylpyrazolium                                                                 0.5     normal                                            salt with 2,4-dibromo-6-iodo-N--                                                                    0.25    >10 <15                                           aci-nitroaniline     0.125   >10 <15                                           2,4,6-Tribromo-N--nitroaniline with                                                                 0.5     >10 <15                                           dibenzylamine        0.25    >20 <35                                                                0.125   normal                                            2,4,6-tribromo-N--nitro-                                                                            0.5     >20 <35                                           aniline with dodecylamine                                                                           0.25    >10 <15                                                                0.125   normal                                            1,1-Dimethylpiperidinium salt with                                                                  0.5     >20 <35                                           2,4,6-tribromo-N--aci-nitroaniline                                                                  0.25    >10 <15                                                                0.125   normal                                            Methyltriphenylphosphonium salt                                                                     0.5     >10 <15                                           with 2,4,6-tribromo-N--aci-nitro-                                                                   0.25    >10 <15                                           aniline              0.125   normal                                            2,4,6-Tribromo-N--nitroaniline,                                                                     0.5     Moderate                                                                       Reduction                                         tetrabutylammonium salt                                                                             0.25    >20 <35                                                                0.125   >20 <35                                           2,4,6-Tribromo-N--nitroaniline,                                                                     0.5     normal                                            sodium salt          0.25    >10 <15                                                                0.125   >10 <15                                           2,4,6-Tribromo-N--nitroaniline,                                                                     0.5     normal                                            potassium salt       0.25    >10 <15                                                                0.125   >10 <15                                           (2-Chloroethyl)trimethyl                                                                            0.5     >10 <15                                           ammonium salt with 2,4,6-                                                                           0.25    normal                                            tribromo-N--aci-nitroaniline                                                                        0.125   >10 <15                                           2,4,6-Tribromo-N--nitroaniline                                                                      0.5     Moderate                                                                       Reduction                                         with ammonia (1:1)   0.25    >10 <15                                                                0.125   >20 <35                                           ______________________________________                                    

EXAMPLE 10 Evaluation of Test Compounds for Enhancing Crop Yield On Cotton

In this experiment cotton plants (Gossypium hirsutum var. "Stoneville") are grown in 20×15 cm fibre pots to the 6th to 7th true leaf stage. They are then sprayed with test solutions or dispersions prepared in water-acetone mixtures containing (1) 0.25% v/v of colloidal Biofilm® surfactant which is a mixture of alkyl aryl polyethoxyethanol, free and combined fatty acids, glycol ethers, dialkylbenzene carboxylate and 2-propanol, and (2) sufficient test compound to provide 1.5, 0.75 or 0.25 kg/ha thereof when applied to said plants from an overhead sprayer designed to deliver 747 l/ha with a moving nozzle over a stationary track. The spray nozzle moves at a constant speed over the test species.

After spraying the plants are placed on greenhouse benches and watered and fertilized in accordance with conventional greenhouse practices. Periodically, the plants are examined, measured, and the number of flower, buds and bolls determined for each plant. Data obtained are reported in table IX below as percent increase in flowers, buds and bolls over untreated controls.

                  TABLE IX                                                         ______________________________________                                         Evaluation of 1,2-Dimethyl-3,5-diphenylpyrazolium                              salt with 2,4,6-Tribromo-N--aci-nitroaniline                                   for Cotton Yield Enhancement                                                   (TREATED AT 6 TO 7TH TRUE LEAF STAGE)                                          ______________________________________                                         Days After                                                                             Rate       % Height  % Increase of Visible                             Treatment                                                                              (Kg/Ha)    Reduction Flowers and Buds                                  ______________________________________                                         33      0.25       --        29.3                                                      0.75       10.1      42.8                                                      1.50       21.8      --                                                42                                                                                     0.25       --        25.9                                                      0.75        9.3       9.3                                                      1.50        7.5      --                                                54                                                                                     0.25       --         9.2                                                      0.75        9.2      33.2                                                      1.50       15.0       9.6                                              ______________________________________                                         Days After                                                                             Rate                  % Increase                                       Treatment                                                                              (Kg/Ha)  Flower Buds  Open Flowers                                                                             Bolls                                  ______________________________________                                         54      0.25     25.6         21.3      62.5                                           0.75     25.6         32.8      41.3                                           1.50     --           29.5      --                                     ______________________________________                                    

EXAMPLE 11 Evaluation of Test Compounds for Enhancing Crop Yield In Sunflowers

In this experiment the procedure of Example 7 was repeated excepting that the crop used was sunflowers, Helianthus annuus DO164 variety, the plants were sprayed three weeks after planting and at the two leaf stage treatments were made at 0.25, 0.125 and 0.0625 kg/ha of test compound.

The plants were held for 63 days after treatment when the number and weight of flowers was determined and recorded. Data obtained are reported in Table X below.

                  TABLE X                                                          ______________________________________                                         Evaluation of 1,2-Dimethyl-3,5-diphenylpyrazolium                              salt with 2,4,6-Tribromo-N--aci-nitroaniline                                   for sunflower yield enhancement                                                (TREATED AT 2 TRUE LEAF STAGE)                                                                               Average                                                                               % Increase                                Days After                                                                              Rate     % Height    Flower of Flower                                 Treatment                                                                               (Kg/Ha)  Reduction   Number Weights                                   ______________________________________                                         63                                                                                       0.0625  --          2.1    45.5                                               0.125    --          3.8     3.7                                               0.250    54.8        9.5    24.0                                      ______________________________________                                    

These data are especially significant since they demonstrate the uniqueness of the pyrazolium salts of the trisubstituted-N-nitroaniline compounds in producing multiple flowering of sunflowers.

EXAMPLE 12 Evaluation of Test Compounds for Enhancing Crop Yield On Soybeans

The procedure of Example 7 was repeated excepting that soybeans (var. Adelphia) were used as the crop plant and plants were treated at the 2nd to 3rd trifoliate stage and held on greenhouse benches for three weeks after treatment. Three weeks after treatment all plants were examined and the number of developed pods counted. Data obtained are reported in Table XI below.

                  TABLE XI                                                         ______________________________________                                         Evaluation of 1,2-Dimethyl-3,5-diphenylpyrazolium                              salt with 2,4,6-tribromo-N--aci-nitroaniline                                   for soybean yield enhancement                                                  (TREATED AT 2ND TO 3RD TRIFOLIATE)                                             Days After Rate     % Increase in                                              Treatment  (Ka/ha)  Pods over untreated controls                               ______________________________________                                         21         0.50     >10                                                                   0.25     >10                                                                   0.125    >10                                                                   0.063    >10                                                        ______________________________________                                    

EXAMPLE 13 Evaluation of the Antilodging Effects of Certain N-Nitroanilines and Salts Thereof on Barley

In this experiment the procedure of Example 7 is repeated excepting that the crop used was barley (Hordeum vulgare, var. Georgie; European lodging prone variety). The plants are treated at the 3-4 leaf stage. Plants are watered prior to treatment and then sprayed to provide the kg/ha rate of test compound desired. After spraying the plants are placed on greenhouse benches and watered and fertilized in accordance with normal greenhouse procedures.

Three weeks after spraying the plants are measured and harvested. All treatments are replicated six times and companions are made against untreated controls. The data obtained are averaged and reported in Table XII below.

The following rating system is used:

5=No increase over controls

4=Slight increase over controls

3=Moderate, significant increase over controls.

                                      TABLE XII                                    __________________________________________________________________________     Evaluation of the antilodging effects of substituted N--nitroanilines in       barley                                                                                                 Height                                                                 Rate                                                                               Phyto-                                                                             in  Tiller                                                                              Stem Weight in g                              Compound        kg/ha                                                                              toxicity                                                                           cm  formation                                                                           stiffness                                                                           Fresh                                                                              Dry                                  __________________________________________________________________________     Control         --  5   53.1                                                                               5    5    49.1                                                                               5.2                                  2,6-Dibromo-N--nitroaniline                                                                    1.0 5   48.3                                                                               3    4    55.8                                                                               5.4                                                  0.5 5   53.0                                                                               3    4    67.5                                                                               6.9                                                  0.25                                                                               5   50.5                                                                               4    4    58.3                                                                               6.2                                  2,6-Dibromo-N--fluoro-N--                                                                      1.0 5   45.2                                                                               4    5    49.2                                                                               --                                   nitroaniline    0.5 5   51.0                                                                               5    5    52.6                                                                               --                                                   0.25                                                                               5   52.0                                                                               4    4    57.8                                                                               6.0                                  1,2-Dibromo-3,5-diphenyl-                                                                      1.0 5   52.3                                                                               3    3    60.4                                                                               5.9                                  pyrazolium salt with 2,6-                                                                      0.5 5   53.3                                                                               5    4    60.7                                                                               6.7                                  dibromo-N--aci-nitroaniline                                                                    0.25                                                                               5   58.2                                                                               5    4    59.2                                                                               6.9                                  Tallowamine compound with 2,6-                                                                 1.0 5   48.7                                                                               4    4    55.9                                                                               --                                   dibromo-N--nitroaniline                                                                        0.5 5   48.5                                                                               4    4    60.1                                                                               7.5                                                  0.25                                                                               5   54.7                                                                               5    4    62.3                                                                               6.8                                  Sodium salt of 2,6-dibromo-N--                                                                 1.0 5   47.0                                                                               3    3    55.5                                                                               --                                   nitroaniline    0.5 5   47.2                                                                               3    4    57.6                                                                               6.4                                                  0.25                                                                               5   50.2                                                                               4    4    55.6                                                                               --                                   2,4-Dibromo-N--nitroaniline                                                                    1.0 5   53.3                                                                               5    5    46.4                                                                               --                                                   0.5 5   56.0                                                                               5    5    56.3                                                                               6.7                                                  0.25                                                                               5   54.7                                                                               4    3    63.5                                                                               7.8                                  2-Bromo-4-cyano-N--nitroaniline                                                                1.0 5   53.2                                                                               5    5    60.9                                                                               7.0                                                  0.5 5   53.3                                                                               4    5    59.2                                                                               7.0                                                  0.25                                                                               5   53.0                                                                               4    5    62.2                                                                               7.4                                  2-Iodo-4,6-dimethyl-N--nitro-                                                                  1.0 5   53.5                                                                               5    5    58.0                                                                               6.2                                  aniline         0.5 5   52.5                                                                               5    5    52.7                                                                               --                                                   0.25                                                                               5   52.7                                                                               5    5    54.1                                                                               --                                   1,2-Dimethyl-3,5-diphenylpyra-                                                                 1.0 5   55.5                                                                               5    5    57.3                                                                               6.0                                  zolium salt with 2,3-dichloro-                                                                 0.5 5   54.7                                                                               5    5    52.6                                                                               --                                   N--aci-nitroaniline                                                                            0.25                                                                               5   56.3                                                                               5    5    51.2                                                                               --                                   Sodium salt with 2,3-dichloro-                                                                 1.0 5   52.2                                                                               5    5    57.5                                                                               6.0                                  N--nitroaniline 0.5 5   53.8                                                                               5    5    58.7                                                                               7.1                                                  0.25                                                                               5   53.3                                                                               5    5    60.9                                                                               8.2                                  Tallowamine compound with 2-                                                                   1.0 5   45.7                                                                               4    4    52.4                                                                               --                                   ethyl-6-isopropyl-N--nitro-                                                                    0.5 5   41.7                                                                               4    4    47.1                                                                               --                                   aniline         0.25                                                                               5   45.0                                                                               4    4    49.2                                                                               --                                   1,2-Dimethyl-3,5-diphenyl-                                                                     1.0 5   50.0                                                                               5    5    47.4                                                                               --                                   pyrazolium salt with 2-Bromo-                                                                  0.5 5   50.6                                                                               5    5    53.5                                                                               --                                   N--aci-nitroaniline                                                                            0.25                                                                               5   52.5                                                                               4    4    51.0                                                                               --                                   2-Ethyl-6-isopropyl-N--nitro-                                                                  1.0 5   51.0                                                                               4    4    56.5                                                                               5.4                                  aniline         0.5 5   48.7                                                                               3    4    59.3                                                                               5.9                                                  0.25                                                                               5   47.7                                                                               4    4    50.5                                                                               --                                   __________________________________________________________________________ 

We claim:
 1. A salt of a substituted N-nitroaniline represented by the structural formula ##STR291## wherein n is an integer of 0 or 1; R₁ is hydrogen or methyl; R₂ and R₆ are halogen, C₁ -C₂ alkyl, CF₃ ; SO₂ R₈ or SR₈ wherein R₈ is C₁ -C₆ alkyl, phenyl, or benzyl and with the proviso that only one of R₂ and R₆ may be F, CF₃, SCH₃, C₂ H₅ or SO₂ C₆ H₅ ; R₃ is hydrogen; R₄ is hydrogen, Br, F, I, CH₃, COC₆ H₅, CN or SO₂ N(CH₃)₂ ; R₅ is hydrogen; X⁺ is organic and represented by structural formula IIIe ##STR292## wherein R_(g) and R_(h) is each methyl or ethyl; R_(i) and R_(k) are phenyl or cyclohexyl; and R_(j) is hydrogen or OCH₃ .
 2. The compound according to claim 1, 1,2-dimethyl-3,5-diphenylpyrazolium salt with 2,4,6-tribromo-N-aci-nitroaniline.
 3. The compound according to claim 1, 1,2-dimethyl-3,5-diphenylpyrazolium salt with 2,6-dibromo-N-aci-nitroaniline.
 4. A compound according to claim 1, wherein R₂ is F, Cl, Br, I, or CF₃ ; R₆ is Cl, Br or I; R₄ is Br, I or hydrogen; and R₁, X⁺, R_(g), R_(h), R_(i), R_(j) and R_(k) are as described in claim
 1. 5. A compound according to claim 1, 1,2-dimethyl-3,5-diphenylpyrazolium salt with 2-bromo-6-iodo-N-aci-nitro aniline.
 6. A compound according to claim 1, 1,2-dimethyl-3,5-diphenylpyrazolium salt with 2-bromo-4,6-diiodo-N-aci-nitroaniline.
 7. A compound according to claim 1, 1,2-dimethyl-3,5-diphenylpyrazolium salt with 2-chloro-4,6-diiodo-N-aci-nitroaniline.
 8. A compound according to claim 1, 1,2-dimethyl-3,5-diphenylpyrazolium salt with 2,6-dichloro-α-methyl-N-aci-nitrobenzylamino.
 9. A compound according to claim 1, 1,2-dimethyl-3,5-diphenylpyrazolium salt with 2,4,6-triiodo-N-aci-nitroaniline.
 10. A compound according to claim 1, 1-ethyl-2-methyl-3,5-diphenylpyrazolium salt with 2,4,6-tribromo-N-aci-nitroaniline.
 11. A compound according to claim 1, 1,2-dimethyl-3,5-diphenylpyrazolium salt with 2,4-dibromo-α-α-α-trifluoro-N-aci-o-toluidine.
 12. A compound according to claim 1, 1,2-dimethyl-3,5-diphenylpyrazolium salt with 2,4-dibromo-6-iodo-N-aci-nitroaniline. 